Leuco compounds, colorant compounds, and compositions containing the same

ABSTRACT

A compound of Formula (I) 
     
       
         
         
             
             
         
       
     
     in which one R p  is —NH 2  and the two remaining R p  are independently selected from the group consisting of —OR 4  and —NR 1 R 4 . A compound of Formula (X) 
     
       
         
         
             
             
         
       
     
     in which one R p  is —NH 2  and the two remaining R p  are independently selected from the group consisting of —OR 4  and —NR 1 R 4 .

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims, pursuant to 35 U.S.C. § 119(e), priority to andthe benefit of the filing date of U.S. Patent Application No. 62/580,211filed on Nov. 1, 2017, the contents of which are hereby incorporated byreference.

TECHNICAL FIELD

This application describes leuco compounds and their correspondingcolored counterparts, laundry care compositions containing suchcompounds, and the use of such compounds in the laundering of textilearticles. These types of compositions can be provided in a stable,substantially colorless state and then may be transformed to an intensecolored state upon exposure to certain physical or chemical changes suchas, for example, exposure to oxygen, ion addition, exposure to light,and the like. The laundry care compositions containing the compounds aredesigned to enhance the apparent or visually perceived whiteness of, orto impart a desired hue to, textile articles washed or otherwise treatedwith the laundry care composition.

BACKGROUND

As textile substrates age, their color tends to fade or yellow due toexposure to light, air, soil, and natural degradation of the fibers thatcomprise the substrates. As such, to visually enhance these textilesubstrates and counteract the fading and yellowing the use of functionaldyes in consumer products has become well known in the prior art. Forexample, it is well known to use whitening agents, either opticalbrighteners or bluing agents, in textile applications. However,traditional whitening agents tend to lose efficacy upon storage due todeleterious interactions with other formulation components (such as, forexample, perfumes). Further, such whitening agents can suffer from poordeposition on textile substrates. As such, formulators tend to increasethe level of whitening agent used to counteract any efficacy lost uponstorage and/or to increase the amount of whitening agent available todeposit on the textile substrate.

Leuco dyes are also known in the prior art to exhibit a change from acolorless or slightly colored state to a colored state upon exposure tospecific chemical or physical triggers. The change in coloration thatoccurs is typically visually perceptible to the human eye. All existingcompounds have some absorbance in the visible light region (400-750 nm),and thus more or less have some color. In this invention, a dye isconsidered as a “leuco dye” if it did not render a significant color atits application concentration and conditions, but renders a significantcolor in its triggered form. The color change upon triggering stems fromthe change of the molar attenuation coefficient (also known as molarextinction coefficient, molar absorption coefficient, and/or molarabsorptivity in some literatures) of the leuco dye molecule in the400-750 nm range, preferably in the 500-650 nm range, and mostpreferably in the 530-620 nm range. The increase of the molarattenuation coefficient of a leuco dye before and after the triggeringshould be greater than 50%, more preferably greater than 200%, and mostpreferably greater than 500%.

Detergent formulations comprising leuco compounds provide theopportunity to deliver measurable whiteness benefits to fabrics uponwashing. These whiteness benefits can depend on several factors, such asthe particular hue imparted to the fabric by the leuco compound afterwashing. Desirable leuco compounds include those that impart a relativehue angle of 210 to 345 to a white cotton fabric. Within that range, arelative hue angle of 270 or greater can, in certain instances bedesirable. However, leuco colorants that exhibit desirable propertiesand can impart this desired range of hues to fabric have provendifficult to come by. Thus, a need still remains for leuco compounds andtheir corresponding colored forms that can impart this desired hue tolaundered fabrics. The compounds of the present invention, whether inthe leuco form or the colored form, are believed to meet this need andto be novel materials that may be profitably employed in detergents forwhitening benefits.

SUMMARY OF THE INVENTION

In a first embodiment, the invention provides a compound of Formula (I)

wherein each individual R_(o) and R_(m) group on each of rings A, B andC is independently selected from the group consisting of hydrogen,deuterium and R⁵;wherein each R⁵ is independently selected from the group consisting ofhalogens, nitro, alkyl, substituted alkyl, aryl, substituted aryl,alkaryl, substituted alkaryl, —(CH₂)_(n)—O—R¹, —(CH₂)_(n)—NR¹R²,—C(O)R¹, —C(O)OR¹, —C(O)O⁻, —C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹,—OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹, —S(O)₂O⁻, —S(O)₂NR¹R², —NR¹C(O)R²,—NR¹C(O)OR², —NR¹C(O)SR², —NR¹C(O)NR²R³, —P(O)₂R¹, —P(O)(OR¹)₂,—P(O)(OR¹)O⁻, and —P(O)(O⁻)₂, wherein the index n is an integer from 0to 4, preferably from 0 to 1, most preferably 0; wherein any two of R¹,R² and R³ attached to the same heteroatom can combine to form a ring offive or more members optionally comprising one or more additionalheteroatoms selected from the group consisting of —O—, —NR¹⁵—, and —S—;wherein G is independently selected from the group consisting ofhydrogen, deuterium, C₁-C₁₆ alkoxide, phenoxide, bisphenoxide, nitrite,alkyl amine, imidazole, arylamine, polyalkylene oxide, halides,alkylsulfide, aryl sulfide, and phosphine oxide;wherein R¹, R², R³, and R¹⁵ are independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, aryl, substitutedaryl, alkaryl, substituted alkaryl, and R⁴; wherein R⁴ is a organicgroup composed of one or more organic monomers with said monomermolecular weights ranging from 28 to 500;wherein one R_(p) is —NH₂ and the two remaining R_(p) are independentlyselected from the group consisting of —OR⁴ and —NR¹R⁴; andwherein any charge present in the compound is balanced with a suitableindependently selected internal or external counterion.

In a second embodiment, the invention provides a compound of Formula (X)

wherein each individual R_(o) and R_(m) group on each of rings A, B andC is independently selected from the group consisting of hydrogen,deuterium and R⁵;wherein each R⁵ is independently selected from the group consisting ofhalogens, nitro, alkyl, substituted alkyl, aryl, substituted aryl,alkaryl, substituted alkaryl, —(CH₂)_(n)—O—R¹, —(CH₂)_(n)—NR¹R²,—C(O)R¹, —C(O)OR¹, —C(O)O⁻, —C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹,—OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹, —S(O)₂O⁻, —S(O)₂NR¹R², —NR¹C(O)R²,—NR¹C(O)OR², —NR¹C(O)SR², —NR¹C(O)NR²R³, —P(O)₂R¹, —P(O)(OR¹)₂,—P(O)(OR)O⁻, and —P(O)(O⁻)₂, wherein the index n is an integer from 0 to4, preferably from 0 to 1, most preferably 0; wherein any two of R¹, R²and R³ attached to the same heteroatom can combine to form a ring offive or more members optionally comprising one or more additionalheteroatoms selected from the group consisting of —O—, —NR¹⁵—, and —S—;wherein R¹, R², R³, and R¹⁵ are independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, aryl, substitutedaryl, alkaryl, substituted alkaryl, and R⁴; wherein R⁴ is a organicgroup composed of one or more organic monomers with said monomermolecular weights ranging from 28 to 500;wherein one R_(p) is —NH₂ and the two remaining R_(p) are independentlyselected from the group consisting of —OR⁴ and —NR¹R⁴; andwherein the charge present in the compound is balanced with a suitableindependently selected internal or external counterion.

DETAILED DESCRIPTION Definitions

As used herein, the term “alkoxy” is intended to include C₁-C₈ alkoxyand alkoxy derivatives of polyols having repeating units such asbutylene oxide, glycidol oxide, ethylene oxide or propylene oxide.

As used herein, the interchangeable terms “alkyleneoxy” and“oxyalkylene,” and the interchangeable terms “polyalkyleneoxy” and“polyoxyalkylene,” generally refer to molecular structures containingone or more than one, respectively, of the following repeating units:—C₂H₄O—, —C₃H₆O—, —C₄H₈O—, and any combinations thereof. Non-limitingstructures corresponding to these groups include —CH₂CH₂O—,—CH₂CH₂CH₂O—, —CH₂CH₂CH₂CH₂O—, —CH₂CH(CH₃)O—, and —CH₂CH(CH₂CH₃)O—, forexample. Furthermore, the polyoxyalkylene constituent may be selectedfrom the group consisting of one or more monomers selected from a C₂₋₂₀alkyleneoxy group, a glycidyl group, or mixtures thereof.

The terms “ethylene oxide,” “propylene oxide” and “butylene oxide” maybe shown herein by their typical designation of “EO,” “PO” and “BO,”respectively.

As used herein, the terms “alkyl” and “alkyl capped” are intended tomean any univalent group formed by removing a hydrogen atom from asubstituted or unsubstituted hydrocarbon. Non-limiting examples includehydrocarbyl moieties which are branched or unbranched, substituted orunsubstituted including C₁-C₁₈ alkyl groups, and in one aspect, C₁-C₆alkyl groups.

As used herein, unless otherwise specified, the term “aryl” is intendedto include C₃-C₁₂ aryl groups. The term “aryl” refers to bothcarbocyclic and heterocyclic aryl groups.

As used herein, the term “alkaryl” refers to any alkyl-substituted arylsubstituents and aryl-substituted alkyl substituents. More specifically,the term is intended to refer to C₇₋₁₆ alkyl-substituted arylsubstituents and C₇₋₁₆ aryl substituted alkyl substituents which may ormay not comprise additional substituents.

As used herein, the term “detergent composition” is a sub-set of laundrycare composition and includes cleaning compositions including but notlimited to products for laundering fabrics. Such compositions may bepre-treatment composition for use prior to a washing step or may berinse added compositions, as well as cleaning auxiliaries, such asbleach additives and “stain-stick” or pre-treat types.

As used herein, the term “laundry care composition” includes, unlessotherwise indicated, granular, powder, liquid, gel, paste, unit dose,bar form and/or flake type washing agents and/or fabric treatmentcompositions, including but not limited to products for launderingfabrics, fabric softening compositions, fabric enhancing compositions,fabric freshening compositions, and other products for the care andmaintenance of fabrics, and combinations thereof. Such compositions maybe pre-treatment compositions for use prior to a washing step or may berinse added compositions, as well as cleaning auxiliaries, such asbleach additives and/or “stain-stick” or pre-treat compositions orsubstrate-laden products such as dryer added sheets.

As used herein, the term “leuco” (as used in reference to, for example,a compound, moiety, radical, dye, monomer, fragment, or polymer) refersto an entity (e.g., organic compound or portion thereof) that, uponexposure to specific chemical or physical triggers, undergoes one ormore chemical and/or physical changes that results in a shift from afirst color state (e.g., uncolored or substantially colorless) to asecond more highly colored state. Suitable chemical or physical triggersinclude, but are not limited to, oxidation, pH change, temperaturechange, and changes in electromagnetic radiation (e.g., light) exposure.Suitable chemical or physical changes that occur in the leuco entityinclude, but are not limited to, oxidation and non-oxidative changes,such as intramolecular cyclization. Thus, in one aspect, a suitableleuco entity can be a reversibly reduced form of a chromophore. In oneaspect, the leuco moiety preferably comprises at least a first and asecond 2-system capable of being converted into a third combinedconjugated t-system incorporating said first and second 2-systems uponexposure to one or more of the chemical and/or physical triggersdescribed above.

As used herein, the terms “leuco composition” or “leuco colorantcomposition” refers to a composition comprising at least two leucocompounds having independently selected structures as described infurther detail herein.

As used herein “average molecular weight” of the leuco colorant isreported as a weight average molecular weight, as determined by itsmolecular weight distribution: as a consequence of their manufacturingprocess, the leuco colorants disclosed herein may contain a distributionof repeating units in their polymeric moiety.

As used herein, the terms “maximum extinction coefficient” and “maximummolar extinction coefficient” are intended to describe the molarextinction coefficient at the wavelength of maximum absorption (alsoreferred to herein as the maximum wavelength), in the range of 400nanometers to 750 nanometers.

As used herein, the term “first color” is used to refer to the color ofthe laundry care composition before triggering, and is intended toinclude any color, including colorless and substantially colorless.

As used herein, the term “second color” is used to refer to the color ofthe laundry care composition after triggering, and is intended toinclude any color that is distinguishable, either through visualinspection or the use of analytical techniques such asspectrophotometric analysis, from the first color of the laundry carecomposition.

As used herein, the term “converting agent” refers to any oxidizingagent as known in the art other than molecular oxygen in any of itsknown forms (singlet and triplet states).

As used herein, the term “triggering agent” refers to a reactantsuitable for converting the leuco composition from a colorless orsubstantially colorless state to a colored state.

As used herein, the term “whitening agent” refers to a dye or a leucocolorant that may form a dye once triggered that when on white cottonprovides a hue to the cloth with a relative hue angle of 210 to 345, oreven a relative hue angle of 240 to 320, or even a relative hue angle of250 to 300 (e.g., 250 to 290).

As used herein, “cellulosic substrates” are intended to include anysubstrate which comprises at least a majority by weight of cellulose.Cellulose may be found in wood, cotton, linen, jute, and hemp.Cellulosic substrates may be in the form of powders, fibers, pulp andarticles formed from powders, fibers and pulp. Cellulosic fibers,include, without limitation, cotton, rayon (regenerated cellulose),acetate (cellulose acetate), triacetate (cellulose triacetate), andmixtures thereof. Articles formed from cellulosic fibers include textilearticles such as fabrics. Articles formed from pulp include paper.

As used herein, articles such as “a” and “an” when used in a claim, areunderstood to mean one or more of what is claimed or described.

As used herein, the terms “include/s” and “including” are meant to benon-limiting.

As used herein, the term “solid” includes granular, powder, bar andtablet product forms.

As used herein, the term “fluid” includes liquid, gel, paste and gasproduct forms.

The test methods disclosed in the Test Methods Section of the presentapplication should be used to determine the respective values of theparameters of Applicants' inventions.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

In one aspect, the molar extinction coefficient of said second coloredstate at the maximum absorbance in the wavelength in the range 200 to1,000 nm (more preferably 400 to 750 nm) is preferably at least fivetimes, more preferably 10 times, even more preferably 25 times, mostpreferably at least 50 times the molar extinction coefficient of saidfirst color state at the wavelength of the maximum absorbance of thesecond colored state. Preferably, the molar extinction coefficient ofsaid second colored state at the maximum absorbance in the wavelength inthe range 200 to 1,000 nm (more preferably 400 to 750 nm) is at leastfive times, preferably 10 times, even more preferably 25 times, mostpreferably at least 50 times the maximum molar extinction coefficient ofsaid first color state in the corresponding wavelength range. Anordinarily skilled artisan will realize that these ratios may be muchhigher. For example, the first color state may have a maximum molarextinction coefficient in the wavelength range from 400 to 750 nm of aslittle as 10 M⁻¹ cm⁻¹, and the second colored state may have a maximummolar extinction coefficient in the wavelength range from 400 to 750 nmof as much as 80,000 M⁻¹ cm¹ or more, in which case the ratio of theextinction coefficients would be 8,000:1 or more.

In one aspect, the maximum molar extinction coefficient of said firstcolor state at a wavelength in the range 400 to 750 nm is less than 1000M⁻¹ cm⁻¹, and the maximum molar extinction coefficient of said secondcolored state at a wavelength in the range 400 to 750 nm is more than5,000 M⁻¹ cm⁻¹, preferably more than 10,000, 25,000, 50,000 or even100,000 M⁻¹ cm⁻¹. A skilled artisan will recognize and appreciate that apolymer comprising more than one leuco moiety may have a significantlyhigher maximum molar extinction coefficient in the first color state(e.g., due to the additive effect of a multiplicity of leuco moieties orthe presence of one or more leuco moieties converted to the secondcolored state).

In another aspect, the lambda max absorption of the chromophore moietyis separated by the emission lambda max of the fluorophore moiety by 1nm, more preferably 25 nm, most preferably 50 nm. In addition, forlaundry care application the emission lambda max is less than theabsorption lambda max of the chromophore

The present invention relates to a class of compounds that may be usefulfor use in laundry care compositions, such as liquid laundry detergent,to provide a blue hue to whiten textile substrates. Leuco colorants arecompounds that are essentially colorless or only lightly colored but arecapable of developing an intense color upon activation. One advantage ofusing leuco compounds in laundry care compositions is that suchcompounds, being colorless until activated, allow the laundry carecomposition to exhibit its own color. The leuco colorant generally doesnot alter the primary color of the laundry care composition. Thus,manufacturers of such compositions can formulate a color that is mostattractive to consumers without concern for added ingredients, such asbluing agents, affecting the final color value of the composition.

The amount of leuco colorant used in the laundry care compositions ofthe present invention may be any level suitable to achieve the aims ofthe invention. In one aspect, the laundry care composition comprisesleuco colorant in an amount from about 0.0001 wt % to about 1.0 wt %,preferably from 0.0005 wt % to about 0.5 wt %, even more preferably fromabout 0.0008 wt % to about 0.2 wt %, most preferably from 0.004 wt % toabout 0.1 wt %.

In another aspect, the laundry care composition comprises leuco colorantin an amount from 0.0025 to 5.0 milliequivalents/kg, preferably from0.005 to 2.5 milliequivalents/kg, even more preferably from 0.01 to 1.0milliequivalents/kg, most preferably from 0.05 to 0.50milliequivalents/kg, wherein the units of milliequivalents/kg refer tothe milliequivalents of leuco moiety per kg of the laundry composition.For leuco colorants comprising more than one leuco moiety, the number ofmilliequivalents is related to the number of millimoles of the leucocolorant by the following equation: (millimoles of leuco colorant)×(no.of milliequivalents of leuco moiety/millimole of leucocolorant)=milliequivalents of leuco moiety. In instances where there isonly a single leuco moiety per leuco colorant, the number ofmilliequivalents/kg will be equal to the number of millimoles of leucocolorant/kg of the laundry care composition.

As noted above, in a first embodiment, the invention provides a compoundof Formula (I)

Further, in a second embodiment, the invention provides a compound ofFormula (X)

The compound of Formula (X) corresponds to the second colored state ofthe leuco compound of Formula (I).

In Formulae (I) and (X), each individual R_(o) and R_(m) group on eachof rings A, B and C is independently selected from the group consistingof hydrogen, deuterium and R⁵. Each R⁵ is independently selected fromthe group consisting of halogens, nitro, alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, substituted alkaryl, —(CH₂)_(n)—O—R¹,—(CH₂)_(n)—NR¹R², —C(O)R¹, —C(O)OR¹, —C(O)O⁻, —C(O)NR¹R², —OC(O)R¹,—OC(O)OR¹, —OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹, —S(O)₂O⁻, —S(O)₂NR¹R²,—NR¹C(O)R², —NR¹C(O)OR², —NR¹C(O)SR², —NR¹C(O)NR²R³, —P(O)₂R¹,—P(O)(OR¹)₂, —P(O)(OR)O⁻, and —P(O)(O⁻)₂. The index n is an integer from0 to 4, preferably from 0 to 1, and most preferably 0. Further, any twoof R¹, R² and R³ attached to the same heteroatom can combine to form aring of five or more members optionally comprising one or moreadditional heteroatoms selected from the group consisting of —O—,—NR¹⁵—, and —S—. In a preferred aspect, all four of the R_(o) and R_(m)on at least one of the rings A, B, and C are hydrogen. In anotherpreferred aspect, all the R_(o) and R_(m) on all three rings A, B, and Care hydrogen.

In Formula (I), the group G is independently selected from the groupconsisting of hydrogen, deuterium, C₁-C₁₆ alkoxide, phenoxide,bisphenoxide, nitrite, alkyl amine, imidazole, arylamine, polyalkyleneoxide, halides, alkylsulfide, aryl sulfide, and phosphine oxide. In oneaspect, G preferably is selected from the group consisting of hydrogenand deuterium. In a more preferred aspect, G is hydrogen.

In Formulae (I) and (X), the groups R¹, R², R³, and R¹⁵ areindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl,and R⁴.

In Formulae (I) and (X), one of the R_(p) attached to one of the ringsA, B, and C is —NH₂, and the two remaining R_(p) are independentlyselected from the group consisting of —OR⁴ and —NR¹R⁴, with R¹ and R⁴being selected from the groups described herein. In a preferred aspect,the two remaining R_(p) are independently selected —NR⁴R⁴.

In Formulae (I) and (X), the group R⁴ is an organic group composed ofone or more organic monomers with said monomer molecular weights rangingfrom 28 to 500, preferably 43 to 350, even more preferably 43 to 250. Inone aspect, R⁴ is selected from the group consisting of—R^(x)—O—R^(y)—R^(z) and —R^(y)—R^(z). The group Rx is selected from thegroup consisting of alkanediyl and arenediyl; and the group R^(z) isselected from the group consisting of hydrogen, alkyl, substitutedalkyl, aryl, substituted aryl, alkaryl, and substituted alkaryl. Thegroup R^(y) is a divalent substituent selected from the group consistingof:

(i) divalent substituents comprising two or more divalent repeatingunits independently selected from repeating units conforming to thestructure of Formula (C)

wherein R¹⁰¹ and R¹⁰² are independently selected from the groupconsisting of hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl, andaryloxyalkyl;

(ii) divalent substituents conforming to the structure of Formula (CX)

wherein R¹¹¹ and R¹¹² are independently selected from the groupconsisting of hydrogen, hydroxy, and C₁-C₁₀ alkyl, aa is an integer from1 to 12, and bb is an integer greater than or equal to 1 (e.g., from 1to 100);

(iii) divalent substituents conforming to the structure of Formula (CXX)

wherein R¹²¹ and R¹²² are independently selected from the groupconsisting of hydrogen, hydroxy, and C₁-C₁₀ alkyl, cc is an integer from1 to 12, and dd is an integer greater than or equal to 1 (e.g., from 1to 100);

(iv) divalent substituents conforming to the structure of Formula (CXXX)

wherein R¹³¹, R¹³², and R¹³³ are independently selected from alkyl andhydroxyalkyl, and ee is an integer greater than or equal to 1 (e.g.,from 1 to 100);

(v) divalent substituents conforming to the structure of Formula (CXL)

wherein each R¹⁴¹ is independently selected from the group consisting ofhydrogen and alkylamine groups, and ff is an integer greater than orequal to 1 (e.g., from 1 to 100);

(vi) divalent substituents conforming to the structure of Formula (CL)

wherein gg is an integer greater than or equal to 1 (e.g., from 1 to100);

(vii) divalent substituents conforming to the structure of Formula (CLX)

wherein each R¹⁶¹ is independently selected from the group consisting ofhydrogen and methyl, and hh is an integer greater than or equal to 1(e.g., from 1 to 100);

(viii) divalent substituents conforming to the structure of Formula(CLXX)

wherein each R¹⁷¹, R¹⁷², and R¹⁷³ is independently selected from thegroup consisting of hydrogen and —CH₂CO₂H, and jj is an integer greaterthan or equal to 1 (e.g., from 1 to 100); and

(ix) divalent substituents comprising two or more substituents selectedfrom the group consisting of substituents conforming to a structure ofFormula (C), (CX), (CXX), (CXXX), (CXL), (CL), (CLX), or (CLXX).

In a preferred aspect, each R⁴ is an independently selected group of theformula (C₂H₄O)_(x)(C₃H₆O)_(y)(C₂H₄O)_(z)R²⁰. The group R²⁰ is selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, and substituted alkaryl. The variables x, y,and z are integers independently selected from 0 and the positivenatural numbers; and the sum of x, y, and z is 1 or more. In one aspect,the variables x, y, and z are independently selected from 0 to 100, morepreferably 0 to 50, even more preferably 0 to 20, and most preferably 0to 10. In a particularly preferred aspect, the variable x is from 1 to5, the variable y is from 0 to 5, and the variable z is 0. In an evenmore preferred aspect, the variable y is from 1 to 5. In anotherpreferred aspect, the variable x is from 1 to 2, the variable y is from0 to 3, and the variable z is 0. In an even more preferred aspect, thevariable y is from 1 to 3. In each of the aspects described above, thegroup R²⁰ preferably is hydrogen.

For the compounds of Formulae (I) and (X), any charge present in thecompound is balanced with a suitable independently selected internal orexternal counterion. Suitable independently selected externalcounterions may be cationic or anionic. Examples of suitable cationsinclude but are not limited to one or more metals preferably selectedfrom Group I and Group II, the most preferred of these being Na, K, Mg,and Ca, or an organic cation such as iminium, ammonium, and phosphonium.Examples of suitable anions include but are not limited to: fluoride,chloride, bromide, iodide, perchlorate, hydrogen sulfate, sulfate,aminosulfate, nitrate, dihydrogen phosphate, hydrogen phosphate,phosphate, bicarbonate, carbonate, methosulfate, ethosulfate, cyanate,thiocyanate, tetrachlorozincate, borate, tetrafluoroborate, acetate,chloroacetate, cyanoacetate, hydroxyacetate, aminoacetate,methylaminoacetate, di- and tri-chloroacetate, 2-chloro-propionate,2-hydroxypropionate, glycolate, thioglycolate, thioacetate,phenoxyacetate, trimethylacetate, valerate, palmitate, acrylate,oxalate, malonate, crotonate, succinate, citrate,methylene-bis-thioglycolate, ethylene-bis-iminoacetate,nitrilotriacetate, fumarate, maleate, benzoate, methylbenzoate,chlorobenzoate, dichlorobenzoate, hydroxybenzoate, aminobenzoate,phthalate, terephthalate, indolylacetate, chlorobenzenesulfonate,benzenesulfonate, toluenesulfonate, biphenyl-sulfonate andchlorotoluenesulfonate. Those of ordinary skill in the art are wellaware of different counterions which can be used in place of thoselisted above.

As depicted in Formula (X), the possesses a positive charge that can, incertain resonance structures, be assigned to the central carbon atom. Asnoted above, the positive charge can be balanced by any suitablyselected internal or external counterion. In one aspect, the positivecharge assigned to the central carbon atom of the compound of Formula(X) is balanced by an external counterion selected from the groupconsisting of halides and sulfates. In another aspect, at least one ofthe R_(o) and R_(m) on at least one of the rings A, B, and C is selectedfrom —C(O)O⁻ and —S(O)₂O⁻, which group provides an internal counterionto balance the positive charge assigned to the central carbon atom ofthe compound of Formula (X).

In one aspect, leuco colorants of the instant invention (e.g., compoundsof Formula (I)) have a Surface Tension Value of greater than 45 mN/m,more preferably greater than 47.5 mN/m, most preferably greater than 50mN/m. In another aspect, the second colored state of the leuco colorant(e.g., a compound of Formula (X)) has a Surface Tension Value of greaterthan 45 mN/m, more preferably greater than 47.5 mN/m, most preferablygreater than 50 mN/m. In yet another aspect of the invention both theleuco colorant and its corresponding second colored state have a SurfaceTension Value of greater than 45 mN/m, more preferably greater than 47.5mN/m, most preferably greater than 50 mN/m.

The compounds and compositions described above are believed to besuitable for use in the treatment of textile materials, such as indomestic laundering processes. In particular, it is believed that thecompounds will deposit onto the fibers of the textile material due tothe nature of the compound. Further, once deposited onto the textilematerial, the leuco versions of these compounds can be converted to acolored compound through the application of the appropriate chemical orphysical triggers that will convert the leuco compound to its coloredform. For example, the leuco compound can be converted to its coloredform upon oxidation of the leuco compound to the oxidized compound. Byselecting the proper leuco moiety, the leuco compound can be designed toimpart a desired hue to the textile material as the leuco compound isconverted to its colored form. For example, a leuco compound thatexhibits a blue or violet hue upon conversion to its colored form can beused to counteract the yellowing of the textile material to normallyoccurs due to the passage of time and/or repeated launderings. Thus, inother embodiments, the invention provides laundry care compositionscomprising the above-described leuco compound and domestic methods fortreating a textile material (e.g., methods for washing an article oflaundry or clothing).

Preferably the compound (e.g., a leuco version of the compound whenconverted to its second color state) gives a hue to the cloth with arelative hue angle of 210 to 345, or even a relative hue angle of 240 to320, or even a relative hue angle of 250 to 300 (e.g., 250 to 290), oreven a relative hue angle of 270 to 300 (e.g., 270 to 290). The relativehue angle can be determined by any suitable method as known in the art.However, preferably it may be determined as described in further detailherein with respect to deposition of the leuco entity on cotton relativeto cotton absent any leuco entity.

In addition to the hueing or whitening effects described above, thecompounds of Formula (X) can be used as aesthetic colorants in laundrycare compositions. In such uses, the compound of Formula (X) can be usedalone or in combination with other aesthetic dyes, pigments, and/orcolorants as described below. Further, when used as an aestheticcolorant, the compound of Formula (X) can be used at any concentrationor loading that imparts the desired aesthetic coloration to the laundrycare composition.

As noted above, in another embodiment, the invention provides a laundrycare composition comprising a laundry care ingredient and a compound asdescribed herein. The laundry care composition can comprise any suitablecompound or combination of compounds as described herein. The laundrycare composition can comprise any suitable laundry care ingredient.Laundry care ingredients suitable for use in the invention are describedin detail below.

Laundry Care Ingredients

The laundry care composition may comprise other suitable adjuncts which,in some aspects, can be wholly or partially incorporated. Adjuncts maybe selected according to the laundry care composition's intendedfunction. The first composition may comprise an adjunct. In someaspects, in the case of multi-compartment unit dose articles, theadjuncts may be part of a non-first (e.g., second, third, fourth, etc.)composition encapsulated in compartments separate from the firstcomposition. The non-first composition may be any suitable composition.The non-first composition may be in the form of a solid, a liquid, adispersion, a gel, a paste or a mixture thereof. Where the unit dosecomprises multiple compartments, the leuco colorant may be added to orpresent in one, two, or even all the compartments. In one embodiment,the leuco colorant is added to the larger compartment, leading to alower concentration which may minimize any issues involved withpotential contact staining. On the other hand, concentrating ananti-oxidant with a leuco colorant in a smaller volume compartment maylead to a higher local concentration of anti-oxidant which may provideenhanced stability. Therefore, as one skilled in the art wouldappreciate, the formulator can select the location and amount of theleuco colorant according to the desired properties of the unit dose.

Adjuncts

The laundry care composition may comprise a surfactant system. Thelaundry care composition may comprise from about 1% to about 80%, orfrom 1% to about 60%, preferably from about 5% to about 50% morepreferably from about 8% to about 40%, by weight of the laundry carecomposition, of a surfactant system

Surfactant: Suitable surfactants include anionic surfactants, non-ionicsurfactant, cationic surfactants, zwitterionic surfactants andamphoteric surfactants and mixtures thereof. Suitable surfactants may belinear or branched, substituted or un-substituted, and may be derivedfrom petrochemical material or biomaterial. Preferred surfactant systemscomprise both anionic and nonionic surfactant, preferably in weightratios from 90:1 to 1:90. In some instances a weight ratio of anionic tononionic surfactant of at least 1:1 is preferred. However a ratio below10:1 may be preferred. When present, the total surfactant level ispreferably from 0.1% to 60%, from 1% to 50% or even from 5% to 40% byweight of the subject composition.Anionic surfactant: Anionic surfactants include, but are not limited to,those surface-active compounds that contain an organic hydrophobic groupcontaining generally 8 to 22 carbon atoms or generally 8 to 18 carbonatoms in their molecular structure and at least one water-solubilizinggroup preferably selected from sulfonate, sulfate, and carboxylate so asto form a water-soluble compound. Usually, the hydrophobic group willcomprise a C₈-C 22 alkyl, or acyl group. Such surfactants are employedin the form of water-soluble salts and the salt-forming cation usuallyis selected from sodium, potassium, ammonium, magnesium and mono-, withthe sodium cation being the usual one chosen.

Anionic surfactants of the present invention and adjunct anioniccosurfactants, may exist in an acid form, and said acid form may beneutralized to form a surfactant salt which is desirable for use in thepresent detergent compositions. Typical agents for neutralizationinclude the metal counterion base such as hydroxides, e.g., NaOH or KOH.Further preferred agents for neutralizing anionic surfactants of thepresent invention and adjunct anionic surfactants or cosurfactants intheir acid forms include ammonia, amines, oligamines, or alkanolamines.Alkanolamines are preferred. Suitable non-limiting examples includingmonoethanolamine, diethanolamine, triethanolamine, and other linear orbranched alkanolamines known in the art; for example, highly preferredalkanolamines include 2-amino-1-propanol, 1-aminopropanol,monoisopropanolamine, or 1-amino-3-propanol. Amine neutralization may bedone to a full or partial extent, e.g. part of the anionic surfactantmix may be neutralized with sodium or potassium and part of the anionicsurfactant mix may be neutralized with amines or alkanolamines.

Suitable sulphonate surfactants include methyl ester sulphonates, alphaolefin sulphonates, alkyl benzene sulphonates, especially alkyl benzenesulphonates, preferably C₁₀₋₁₃ alkyl benzene sulphonate. Suitable alkylbenzene sulphonate (LAS) is obtainable, preferably obtained, bysulphonating commercially available linear alkyl benzene (LAB). SuitableLAB includes low 2-phenyl LAB, such as those supplied by Sasol under thetradename Isochem® or those supplied by Petresa under the tradenamePetrelab®, other suitable LAB include high 2-phenyl LAB, such as thosesupplied by Sasol under the tradename Hyblene®. A suitable anionicsurfactant is alkyl benzene sulphonate that is obtained by DETALcatalyzed process, although other synthesis routes, such as HF, may alsobe suitable. In one aspect a magnesium salt of LAS is used.

Suitable sulphate surfactants include alkyl sulphate, preferably C₈₋₁₈alkyl sulphate, or predominantly C₁₂ alkyl sulphate.

A preferred sulphate surfactant is alkyl alkoxylated sulphate,preferably alkyl ethoxylated sulphate, preferably a C₈₋₁₈ alkylalkoxylated sulphate, preferably a C₈₋₁₈ alkyl ethoxylated sulphate,preferably the alkyl alkoxylated sulphate has an average degree ofalkoxylation of from 0.5 to 20, preferably from 0.5 to 10, preferablythe alkyl alkoxylated sulphate is a C₈₋₁₈ alkyl ethoxylated sulphatehaving an average degree of ethoxylation of from 0.5 to 10, preferablyfrom 0.5 to 5, more preferably from 0.5 to 3. The alkyl alkoxylatedsulfate may have a broad alkoxy distribnution or a peaked alkoxydistribution.

The alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzenesulphonates may be linear or branched, including 2 alkyl substituted ormid chain branched type, substituted or un-substituted, and may bederived from petrochemical material or biomaterial. Preferably, thebranching group is an alkyl. Typically, the alkyl is selected frommethyl, ethyl, propyl, butyl, pentyl, cyclic alkyl groups and mixturesthereof. Single or multiple alkyl branches could be present on the mainhydrocarbyl chain of the starting alcohol(s) used to produce thesulfated anionic surfactant used in the detergent of the invention. Mostpreferably the branched sulfated anionic surfactant is selected fromalkyl sulfates, alkyl ethoxy sulfates, and mixtures thereof.

Alkyl sulfates and alkyl alkoxy sulfates are commercially available witha variety of chain lengths, ethoxylation and branching degrees.Commercially available sulfates include those based on Neodol alcoholsex the Shell company, Lial—Isalchem and Safol ex the Sasol company,natural alcohols ex The Procter & Gamble Chemicals company.

Other suitable anionic surfactants include alkyl ether carboxylates.

Non-ionic surfactant: Suitable non-ionic surfactants are selected fromthe group consisting of: C₈-C₁₈ alkyl ethoxylates, such as, NEODOL®non-ionic surfactants from Shell; C₆-C₁₂ alkyl phenol alkoxylateswherein preferably the alkoxylate units are ethyleneoxy units,propyleneoxy units or a mixture thereof; C₁₂-C₁₈ alcohol and C₆-C₁₂alkyl phenol condensates with ethylene oxide/propylene oxide blockpolymers such as Pluronic® from BASF; alkylpolysaccharides, preferablyalkylpolyglycosides; methyl ester ethoxylates; polyhydroxy fatty acidamides; ether capped poly(oxyalkylated) alcohol surfactants; andmixtures thereof.

Suitable non-ionic surfactants are alkylpolyglucoside and/or an alkylalkoxylated alcohol.

Suitable non-ionic surfactants include alkyl alkoxylated alcohols,preferably C₈₋₁₈ alkyl alkoxylated alcohol, preferably a C₈₋₁₈ alkylethoxylated alcohol, preferably the alkyl alkoxylated alcohol has anaverage degree of alkoxylation of from 1 to 50, preferably from 1 to 30,or from 1 to 20, or from 1 to 10, preferably the alkyl alkoxylatedalcohol is a C₈-18 alkyl ethoxylated alcohol having an average degree ofethoxylation of from 1 to 10, preferably from 1 to 7, more preferablyfrom 1 to 5 and most preferably from 3 to 7. In one aspect, the alkylalkoxylated alcohol is a C₁₂₋₁₅ alkyl ethoxylated alcohol having anaverage degree of ethoxylation of from 7 to 0. The alkyl alkoxylatedalcohol can be linear or branched, and substituted or un-substituted.Suitable nonionic surfactants include those with the trade nameLutensol® from BASF.

Cationic surfactant: Suitable cationic surfactants include alkylpyridinium compounds, alkyl quaternary ammonium compounds, alkylquaternary phosphonium compounds, alkyl ternary sulphonium compounds,and mixtures thereof.

Preferred cationic surfactants are quaternary ammonium compounds havingthe general formula:

(R)(R₁)(R₂)(R₃)N⁺X⁻

wherein, R is a linear or branched, substituted or unsubstituted C₆₋₁₈alkyl or alkenyl moiety, R₁ and R₂ are independently selected frommethyl or ethyl moieties, R₃ is a hydroxyl, hydroxymethyl or ahydroxyethyl moiety, X is an anion which provides charge neutrality,preferred anions include: halides, preferably chloride; sulphate; andsulphonate.Amphoteric and Zwitterionic surfactant: Suitable amphoteric orzwitterionic surfactants include amine oxides, and/or betaines.Preferred amine oxides are alkyl dimethyl amine oxide or alkyl amidopropyl dimethyl amine oxide, more preferably alkyl dimethyl amine oxideand especially coco dimethyl amino oxide. Amine oxide may have a linearor mid-branched alkyl moiety. Typical linear amine oxides includewater-soluble amine oxides containing one R1 C8-18 alkyl moiety and 2 R2and R3 moieties selected from the group consisting of C1-3 alkyl groupsand C1-3 hydroxyalkyl groups. Preferably amine oxide is characterized bythe formula R1-N(R2)(R3) O wherein R1 is a C8-18 alkyl and R2 and R3 areselected from the group consisting of methyl, ethyl, propyl, isopropyl,2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl. The linear amineoxide surfactants in particular may include linear C10-C18 alkyldimethyl amine oxides and linear C8-C12 alkoxy ethyl dihydroxy ethylamine oxides.

Other suitable surfactants include betaines, such as alkyl betaines,alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (INCI Sultaines)as well as Phosphobetaines.

Leuco Colorant Diluent

Another class of ingredients in the leuco colorants composition may be adiluent and/or solvent. The purpose of the diluent and/or solvent isoften, but not limited to, improving fluidity and/or reducing theviscosity of the leuco colorant. Although water is often the preferreddiluent and/or solvent given its low cost and non-toxicity, othersolvent may also be used as well. The preferred solvent is one havinglow cost and low hazards. Examples of suitable solvents include, but arenot limited to, ethylene glycol, propylene glycol, glycerin, alkoxylatedpolymers such as polyethylene glycol, polypropylene glycol, copolymersof ethylene oxide and propylene oxide, Tween 20@, Tween 40®, Tween 80®,and the like, and combinations thereof. Among the polymers, the ethyleneoxide and propylene oxide copolymers may be preferred. These polymersoften feature a cloud point with water, which can help the productseparated from the water to remove the undesirable water solubleimpurities. Examples of ethylene oxide and propylene oxide copolymersinclude but not limited to the PLURONIC series polymers by BASF andTERGITOL™ series polymer and by Dow. When the leuco colorant compositionis incorporated into the laundry care composition, these polymers mayalso act as a non-ionic surfactant.

The laundry care compositions described herein may also include one ormore of the following non-limiting list of ingredients: fabric carebenefit agent; detersive enzyme; deposition aid; rheology modifier;builder; chelant; bleach; bleaching agent; bleach precursor; bleachbooster; bleach catalyst; perfume and/or perfume microcapsules; perfumeloaded zeolite; starch encapsulated accord; polyglycerol esters;whitening agent; pearlescent agent; enzyme stabilizing systems;scavenging agents including fixing agents for anionic dyes, complexingagents for anionic surfactants, and mixtures thereof; opticalbrighteners or fluorescers; polymer including but not limited to soilrelease polymer and/or soil suspension polymer; dispersants; antifoamagents; non-aqueous solvent; fatty acid; suds suppressors, e.g.,silicone suds suppressors; cationic starches; scum dispersants;substantive dyes; colorants; opacifier; antioxidant; hydrotropes such astoluenesulfonates, cumenesulfonates and naphthalenesulfonates; colorspeckles; colored beads, spheres or extrudates; clay softening agents;anti-bacterial agents. Additionally or alternatively, the compositionsmay comprise surfactants, quaternary ammonium compounds, and/or solventsystems. Quaternary ammonium compounds may be present in fabric enhancercompositions, such as fabric softeners, and comprise quaternary ammoniumcations that are positively charged polyatomic ions of the structure NR₄⁺, where R is an alkyl group or an aryl group

Hueing Dye

The composition may comprise an additional fabric shading agent.Suitable fabric shading agents include dyes, dye-clay conjugates, andpigments. Suitable dyes include small molecule dyes and polymeric dyes.Suitable small molecule dyes include small molecule dyes selected fromthe group consisting of dyes falling into the Colour Index (C.I.)classifications of Direct Blue, Direct Red, Direct Violet, Acid Blue,Acid Red, Acid Violet, Basic Blue, Basic Violet and Basic Red, ormixtures thereof. Preferered dyes include alkoxylated azothiophenes,Solvent Violet 13, Acid Violet 50 and Direct Violet 9.

Aesthetic Colorants. The composition may comprise one or more aestheticcolorants. Suitable aesthetic colorants include dyes, dye-clayconjugates, pigments, and Liquitint® polymeric colorants (Milliken &Company, Spartanburg, S.C., USA). In one aspect, suitable dyes andpigments include small molecule dyes and polymeric dyes. The aestheticcolorant may include at least one chromophore constituent selected fromthe group consisting of acridines, anthraquinones, azines, azos,benzodifuranes, benzodifuranones, carotenoids, coumarins, cyanines,diazahemicyanines, diphenylmethanes, formazans, hemicyanines, indigoids,methanes, methines, naphthalimides, naphthoquinones, nitros, nitrosos,oxazines, phenothiazine, phthalocyanines (such as copperphthalocyanines), pyrazoles, pyrazolones, quinolones, stilbenes,styryls, triarylmethanes (such as triphenylmethanes), xanthenes, andmixtures thereof.

In one aspect of the invention, aesthetic colorants include Liquitint®Blue AH, Liquitint® Blue BB, Liquitint® Blue 275, Liquitint® Blue 297,Liquitint® Blue BB, Cyan 15, Liquitint® Green 101, Liquitint® Orange272, Liquitint® Orange 255, Liquitint® Pink AM, Liquitint® Pink AMC,Liquitint® Pink ST, Liquitint® Violet 129, Liquitint® Violet LS,Liquitint® Violet 291, Liquitint® Yellow FT, Liquitint® Blue Buf,Liquitint® Pink AM, Liquitint® Pink PV, Acid Blue 80, Acid Blue 182,Acid Red 33, Acid Red 52, Acid Violet 48, Acid Violet 126, Acid Blue 9,Acid Blue 1, and mixtures thereof.

Encapsulates. The composition may comprise an encapsulated material. Inone aspect, an encapsulate comprising a core, a shell having an innerand outer surface, said shell encapsulating said core. The core maycomprise any laundry care adjunct, though typically the core maycomprise material selected from the group consisting of perfumes;brighteners; hueing dyes; insect repellants; silicones; waxes; flavors;vitamins; fabric softening agents; skin care agents in one aspect,paraffins; enzymes; anti-bacterial agents; bleaches; sensates; andmixtures thereof; and said shell may comprise a material selected fromthe group consisting of polyethylenes; polyamides; polyvinylalcohols,optionally containing other co-monomers; polystyrenes; polyisoprenes;polycarbonates; polyesters; polyacrylates; aminoplasts, in one aspectsaid aminoplast may comprise a polyureas, polyurethane, and/orpolyureaurethane, in one aspect said polyurea may comprisepolyoxymethyleneurea and/or melamine formaldehyde; polyolefins;polysaccharides, in one aspect said polysaccharide may comprise alginateand/or chitosan; gelatin; shellac; epoxy resins; vinyl polymers; waterinsoluble inorganics; silicone; and mixtures thereof.

Preferred encapsulates comprise perfume. Preferred encapsulates comprisea shell which may comprise melamine formaldehyde and/or cross linkedmelamine formaldehyde. Other preferred capsules comprise a polyacrylatebased shell. Preferred encapsulates comprise a core material and ashell, said shell at least partially surrounding said core material, isdisclosed. At least 75%, 85% or even 90% of said encapsulates may have afracture strength of from 0.2 MPa to 10 MPa, and a benefit agent leakageof from 0% to 20%, or even less than 10% or 5% based on total initialencapsulated benefit agent. Preferred are those in which at least 75%,85% or even 90% of said encapsulates may have (i) a particle size offrom 1 microns to 80 microns, 5 microns to 60 microns, from 10 micronsto 50 microns, or even from 15 microns to 40 microns, and/or (ii) atleast 75%, 85% or even 90% of said encapsulates may have a particle wallthickness of from 30 nm to 250 nm, from 80 nm to 180 nm, or even from100 nm to 160 nm. Formaldehyde scavengers may be employed withencapsulates, for example, in a capsule slurry and/or added to acomposition before, during or after the encapsulates are added to suchcomposition. Suitable capsules that can be made by following theteaching of USPA 2008/0305982 A1; and/or USPA 2009/0247449 A1.Alternatively, suitable capsules can be purchased from Appleton PapersInc. of Appleton, Wis. USA.

In a preferred aspect the composition may comprise a deposition aid,preferably in addition to encapsulates. Preferred deposition aids areselected from the group consisting of cationic and nonionic polymers.Suitable polymers include cationic starches, cationichydroxyethylcellulose, polyvinylformaldehyde, locust bean gum, mannans,xyloglucans, tamarind gum, polyethyleneterephthalate and polymerscontaining dimethylaminoethyl methacrylate, optionally with one or moremonomers selected from the group comprising acrylic acid and acrylamide.

Perfume. Preferred compositions of the invention comprise perfume.Typically the composition comprises a perfume that comprises one or moreperfume raw materials, selected from the group as described inWO08/87497. However, any perfume useful in a laundry care compositionmay be used. A preferred method of incorporating perfume into thecompositions of the invention is via an encapsulated perfume particlecomprising either a water-soluble hydroxylic compound ormelamine-formaldehyde or modified polyvinyl alcohol.

Malodor Reduction Materials

The cleaning compositions of the present disclosure may comprisemalodour reduction materials. Such materials are capable of decreasingor even eliminating the perception of one or more malodors. Thesematerials can be characterized by a calculated malodor reduction value(“MORV”), which is calculated according to the test method shown inWO2016/049389.

As used herein “MORV” is the calculated malodor reduction value for asubject material. A material's MORV indicates such material's ability todecrease or even eliminate the perception of one or more malodors.

The cleaning compositions of the present disclosure may comprise a sumtotal of from about 0.00025% to about 0.5%, preferably from about0.0025% to about 0.1%, more preferably from about 0.005% to about0.075%, most preferably from about 0.01% to about 0.05%, by weight ofthe composition, of 1 or more malodor reduction materials. The cleaningcomposition may comprise from about 1 to about 20 malodor reductionmaterials, more preferably 1 to about 15 malodor reduction materials,most preferably 1 to about 10 malodor reduction materials.

One, some, or each of the malodor reduction materials may have a MORV ofat least 0.5, preferably from 0.5 to 10, more preferably from 1 to 10,most preferably from 1 to 5. One, some, or each of the malodor reductionmaterials may have a Universal MORV, defined as all of the MORV valuesof >0.5 for the malodors tested as described herein. The sum total ofmalodor reduction materials may have a Blocker Index of less than 3,more preferable less than about 2.5, even more preferably less thanabout 2, and still more preferably less than about 1, and mostpreferably about 0. The sum total of malodor reduction materials mayhave a Blocker Index average of from about 3 to about 0.001.

In the cleaning compositions of the present disclosure, the malodorreduction materials may have a Fragrance Fidelity Index of less than 3,preferably less than 2, more preferably less than 1 and most preferablyabout 0 and/or a Fragrance Fidelity Index average of 3 to about 0.001Fragrance Fidelity Index. As the Fragrance Fidelity Index decreases, themalodor reduction material(s) provide less and less of a scent impact,while continuing to counteract malodors.

The cleaning compositions of the present disclosure may comprise aperfume. The weight ratio of parts of malodor reduction composition toparts of perfume may be from about 1:20,000 to about 3000:1, preferablyfrom about 1:10,000 to about 1,000:1, more preferably from about 5,000:1to about 500:1, and most preferably from about 1:15 to about 1:1. As theratio of malodor reduction composition to parts of perfume is tightened,the malodor reduction material(s) provide less and less of a scentimpact, while continuing to counteract malodors.

Tannins

The cleaning compositions of the present disclosure may comprisetannins. Tannins are polyphenolic secondary metabolites of higherplants, and are either galloyl esters and their derivatives, in whichgalloyl moieties or their derivatives are attached to a variety ofpolyol-, catechin- and triterpenoid cores (gallotannis, ellagitanninsand complex tannins), or they are oligomeric and polymericproanthocyanidis that can possess interflavanyl coupling andsubstitution patterns (condensed tannins). The cleaning compositions ofthe present disclosure may comprise tannins selected from the groupconsisting of gallotannins, ellagitannins, complex tannins, condensedtannins, and combinations thereof

Polymers. The composition may comprise one or more polymers. Examplesare optionally modified carboxymethylcellulose, poly(vinyl-pyrrolidone),poly (ethylene glycol), poly(vinyl alcohol),poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates suchas polyacrylates, maleic/acrylic acid copolymers and laurylmethacrylate/acrylic acid co-polymers.

The composition may comprise one or more amphiphilic cleaning polymers.Such polymers have balanced hydrophilic and hydrophobic properties suchthat they remove grease particles from fabrics and surfaces. Suitableamphiphilic alkoxylated grease cleaning polymers comprise a corestructure and a plurality of alkoxylate groups attached to that corestructure. These may comprise alkoxylated polyalkylenimines, especiallyethoxylated polyethylene imines or polyethyleneimines having an innerpolyethylene oxide block and an outer polypropylene oxide block.Typically these may be incorporated into the compositions of theinvention in amounts of from 0.005 to 10 wt %, generally from 0.5 to 8wt %.

The composition may comprise a modified hexamethylenediamine. Themodification of the hexamethylenediamine includes: (1) one or twoalkoxylation modifications per nitrogen atom of thehexamethylenediamine. The alkoxylation modification consisting of thereplacement of a hydrogen atom on the nitrogen of thehexamethylenediamine by a (poly)alkoxylene chain having an average ofabout 1 to about 40 alkoxy moieties per modification, wherein theterminal alkoxy moiety of the alkoxylene chain is capped with hydrogen,a C1-C4 alkyl, sulfates, carbonates, or mixtures thereof; (2) asubstitution of one C1-C4 alkyl moiety and one or two alkoxylationmodifications per nitrogen atom of the hexamethylenediamine. Thealkoxylation modification consisting of the replacement of a hydrogenatom by a (poly)alkoxylene chain having an average of about 1 to about40 alkoxy moieties per modification wherein the terminal alkoxy moietyof the alkoxylene chain is capped with hydrogen, a C1-C4 alkyl ormixtures thereof; or (3) a combination thereof

Alkoxylated polycarboxylates such as those prepared from polyacrylatesare useful herein to provide additional grease removal performance. Suchmaterials are described in WO 91/08281 and PCT 90/01815. Chemically,these materials comprise polyacrylates having one ethoxy side-chain perevery 7-8 acrylate units. The side-chains are of the formula—(CH₂CH₂O)_(m) (CH₂)_(n)CH₃ wherein m is 2-3 and n is 6-12. Theside-chains are ester-linked to the polyacrylate “backbone” to provide a“comb” polymer type structure. The molecular weight can vary, but istypically in the range of about 2000 to about 50,000. Such alkoxylatedpolycarboxylates can comprise from about 0.05% to about 10%, by weight,of the compositions herein.

Another suitable carboxylate polymer is a co-polymer that comprises: (i)from 50 to less than 98 wt % structural units derived from one or moremonomers comprising carboxyl groups; (ii) from 1 to less than 49 wt %structural units derived from one or more monomers comprising sulfonatemoieties; and (iii) from 1 to 49 wt % structural units derived from oneor more types of monomers selected from ether bond-containing monomersrepresented by formulas (I) and (II):

wherein in formula (I), R₀ represents a hydrogen atom or CH₃ group, Rrepresents a CH₂ group, CH₂CH₂ group or single bond, X represents anumber 0-5 provided X represents a number 1-5 when R is a single bond,and R₁ is a hydrogen atom or C₁ to C₂₀ organic group;

wherein in formula (II), R₀ represents a hydrogen atom or CH₃ group, Rrepresents a CH₂ group, CH₂CH₂ group or single bond, X represents anumber 0-5, and R₁ is a hydrogen atom or C₁ to C₂₀ organic group.

It may be preferred that the polymer has a weight average molecularweight of at least 50 kDa, or even at least 70 kDa.

Other suitable polymers include amphiphilic graft copolymers. Preferredamphiphilic graft co-polymer(s) comprise (i) polyethyelene glycolbackbone; and (ii) and at least one pendant moiety selected frompolyvinyl acetate, polyvinyl alcohol and mixtures thereof. A preferredamphiphilic graft co-polymer is Sokalan HP22, supplied from BASF. Othersuitable polymers include random graft copolymers, preferably apolyvinyl acetate grafted polyethylene oxide copolymer having apolyethylene oxide backbone and multiple polyvinyl acetate side chains.The molecular weight of the polyethylene oxide backbone is preferablyabout 6000 and the weight ratio of the polyethylene oxide to polyvinylacetate is about 40 to 60 and no more than 1 grafting point per 50ethylene oxide units. Typically these are incorporated into thecompositions of the invention in amounts from 0.005 to 10 wt %, moreusually from 0.05 to 8 wt %.

The composition may comprise one or more soil release polymers. Examplesinclude soil release polymers having a structure as defined by one ofthe following Formula (VI), (VII) or (VIII):

—[(OCHR¹—CHR²)_(a)—O—OC—Ar—CO—]_(d)  (VI)

—[(OCHR³—CHR⁴)_(b)—O—OC-sAr—CO—]_(e)  (VII)

—[(OCHR⁵—CHR⁶)_(c)—OR⁷]_(f)  (VIII)

wherein:a, b and c are from 1 to 200;d, e and f are from 1 to 50;Ar is a 1,4-substituted phenylene;sAr is 1,3-substituted phenylene substituted in position 5 with SO₃Me;Me is Li, K, Mg/2, Ca/2, A1/3, ammonium, mono-, di-, tri-, ortetraalkylammonium wherein the alkyl groups are C₁-C₁₈ alkyl or C₂-C₁₀hydroxyalkyl, or mixtures thereof;R¹, R², R³, R⁴, R⁵ and R⁶ are independently selected from H or C₁-C₁₈ n-or iso-alkyl; andR⁷ is a linear or branched C₁-C₁₈ alkyl, or a linear or branched C₂-C₃₀alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C₈-C₃₀aryl group, or a C₆-C₃₀ arylalkyl group.

Suitable soil release polymers are polyester soil release polymers suchas Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6supplied by Rhodia. Other suitable soil release polymers include Texcarepolymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240,SRN300 and SRN325 supplied by Clariant. Other suitable soil releasepolymers are Marloquest polymers, such as Marloquest SL supplied bySasol.

The composition may also comprise one or more cellulosic polymer,including those selected from alkyl cellulose, alkyl alkoxyalkylcellulose, carboxyalkyl cellulose, alkyl carboxyalkyl cellulose.

Preferred cellulosic polymers are selected from the group comprisingcarboxymethyl cellulose, methyl cellulose, methyl hydroxyethylcellulose, methyl carboxymethyl cellulose, and mixures thereof. In oneaspect, the carboxymethyl cellulose has a degree of carboxymethylsubstitution from 0.5 to 0.9 and a molecular weight from 100,000 Da to300,000 Da.

Soil release polymer: The composition may comprise a soil releasepolymer. A suitable soil release polymer has a structure as defined byone of the following structures (I), (II) or (III):

—[(OCHR¹—CHR²)_(a)—O—OC—Ar—CO—]_(d)  (I)

—[(OCHR³—CHR⁴)_(b)—O—OC-sAr—CO—]_(e)  (II)

—[(OCHR⁵—CHR⁶)_(c)—OR⁷]_(f)  (III)

wherein:a, b and c are from 1 to 200;d, e and f are from 1 to 50;Ar is a 1,4-substituted phenylene;sAr is 1,3-substituted phenylene substituted in position 5 with SO₃Me;Me is Li, K, Mg/2, Ca/2, A1/3, ammonium, mono-, di-, tri-, ortetraalkylammonium wherein the alkyl groups are C₁-C₁₈ alkyl or C₂-C₁₀hydroxyalkyl, or mixtures thereof;R¹, R², R³, R⁴, R⁵ and R⁶ are independently selected from H or C₁-C₁₈ n-or iso-alkyl; andR⁷ is a linear or branched C₁-C₁₈ alkyl, or a linear or branched C₂-C₃₀alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C₈-C₃₀aryl group, or a C₆-C₃₀ arylalkyl group. Suitable soil release polymersare sold by Clariant under the TexCare® series of polymers, e.g.TexCare® SRN240 and TexCare® SRA300. Other suitable soil releasepolymers are sold by Solvay under the Repel-o-Tex® series of polymers,e.g. Repel-o-Tex® SF2 and Repel-o-Tex@Crystal.

Known polymeric soil release agents, hereinafter “SRA” or “SRA's”, canoptionally be employed in the present detergent compositions. Ifutilized, SRA's will generally comprise from 0.01% to 10.0%, typicallyfrom 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of thecomposition.

Preferred SRA's typically have hydrophilic segments to hydrophilize thesurface of hydrophobic fibers such as polyester and nylon, andhydrophobic segments to deposit upon hydrophobic fibers and remainadhered thereto through completion of washing and rinsing cycles therebyserving as an anchor for the hydrophilic segments. This can enablestains occurring subsequent to treatment with SRA to be more easilycleaned in later washing procedures.

SRA's can include, for example, a variety of charged, e.g., anionic oreven cationic (see U.S. Pat. No. 4,956,447), as well as nonchargedmonomer units and structures may be linear, branched or evenstar-shaped. They may include capping moieties which are especiallyeffective in controlling molecular weight or altering the physical orsurface-active properties. Structures and charge distributions may betailored for application to different fiber or textile types and forvaried detergent or detergent additive products. Suitable soil releasepolymers are polyester soil release polymers such as Repel-o-texpolymers, including Repel-o-tex, SF-2 and SRP6 supplied by Rhodia. Othersuitable soil release polymers include Texcare polymers, includingTexcare SRA100, SRA300, SRN100, SRN170, SRN240, SRN300 and SRN325supplied by Clariant. Other suitable soil release polymers areMarloquest polymers, such as Marloquest SL supplied by Sasol Examples ofSRAs are described in U.S. Pat. Nos. 4,968,451; 4,711,730; 4,721,580;4,702,857; 4,877,896; 3,959,230; 3,893,929; 4,000,093; 5,415,807;4,201,824; 4,240,918; 4,525,524; 4,201,824; 4,579,681; and 4,787,989;European Patent Application 0 219 048; 279,134 A; 457,205 A; and DE2,335,044.

Carboxylate polymer: The composition may comprise a carboxylate polymer,such as a maleate/acrylate random copolymer or polyacrylate homopolymer.Suitable carboxylate polymers include: polyacrylate homopolymers havinga molecular weight of from 4,000 Da to 9,000 Da; maleate/acrylate randomcopolymers having a molecular weight of from 50,000 Da to 100,000 Da, orfrom 60,000 Da to 80,000 Da.

Alternatively, these materials may comprise polyacrylates having oneethoxy side-chain per every 7-8 acrylate units. The side-chains are ofthe formula —(CH₂CH₂O)_(m) (CH₂)_(n)CH₃ wherein m is 2-3 and n is 6-12.The side-chains are ester-linked to the polyacrylate “backbone” toprovide a “comb” polymer type structure. The molecular weight can vary,but is typically in the range of about 2000 to about 50,000. Suchalkoxylated polycarboxylates can comprise from about 0.05% to about 10%,by weight, of the compositions herein.

Another suitable carboxylate polymer is a co-polymer that comprises: (i)from 50 to less than 98 wt % structural units derived from one or moremonomers comprising carboxyl groups; (ii) from 1 to less than 49 wt %structural units derived from one or more monomers comprising sulfonatemoieties; and (iii) from 1 to 49 wt % structural units derived from oneor more types of monomers selected from ether bond-containing monomersrepresented by formulas (I) and (II):

wherein in formula (I), R₀ represents a hydrogen atom or CH₃ group, Rrepresents a CH₂ group, CH₂CH₂ group or single bond, X represents anumber 0-5 provided X represents a number 1-5 when R is a single bond,and R₁ is a hydrogen atom or C₁ to C₂₀ organic group;

wherein in formula (II), R₀ represents a hydrogen atom or CH₃ group, Rrepresents a CH₂ group, CH₂CH₂ group or single bond, X represents anumber 0-5, and R₁ is a hydrogen atom or C₁ to C₂₀ organic group.

It may be preferred that the polymer has a weight average molecularweight of at least 50 kDa, or even at least 70 kDa.

Such carboxylate based polymers can advantageously be utilized at levelsfrom about 0.1% to about 7%, by weight, in the compositions herein.Suitable polymeric dispersing agents include carboxylate polymer such asa maleate/acrylate random copolymer or polyacrylate homopolymer.Preferably the carboxylate polymer is a polyacrylate homopolymer havinga molecular weight of from 4,000 Daltons to 9,000 Daltons, ormaleate/acrylate copolymer with a molecular weight 60,000 Daltons to80,000 Daltons. Polymeric polycarboxylates and polyethylene glycols, canalso be used. Polyalkylene glycol-based graft polymer may prepared fromthe polyalkylene glycol-based compound and the monomer material, whereinthe monomer material includes the carboxyl group-containing monomer andthe optional additional monomer(s). Optional additional monomers notclassified as a carboxyl group-containing monomer include sulfonic acidgroup-containing monomers, amino group-containing monomers, allylaminemonomers, quaternized allylamine monomers, N vinyl monomers, hydroxylgroup-containing monomers, vinylaryl monomers, isobutylene monomers,vinyl acetate monomers, salts of any of these, derivatives of any ofthese, and mixtures thereof. It is believed, though it is not intendedto be limited by theory, that polymeric dispersing agents enhanceoverall detergent builder performance, when used in combination withother builders (including lower molecular weight polycarboxylates) bycrystal growth inhibition, particulate soil release peptization, andanti-redeposition. Examples of polymeric dispersing agents are found inU.S. Pat. No. 3,308,067, European Patent Application No. 66915, EP193,360, and EP 193,360.

Alkoxylated polyamine based polymers: The composition may comprissealkoxylated polyamines. Such materials include but are not limited toethoxylated polyethyleneimine, ethoxylated hexamethylene diamine, andsulfated versions thereof. Polypropoxylated derivatives are alsoincluded. A wide variety of amines and polyaklyeneimines can bealkoxylated to various degrees, and optionally further modified toprovide the abovementioned benefits. A useful example is 600 g/molpolyethyleneimine core ethoxylated to 20 EO groups per NH and isavailable from BASF.

Useful alkoxylated polyamine based polymers include the alkoxylatedpolyethylene imine type where said alkoxylated polyalkyleneimine has apolyalkyleneimine core with one or more side chains bonded to at leastone nitrogen atom in the polyalkyleneimine core, wherein saidalkoxylated polyalkyleneimine has an empirical formula (I) of(PEI)_(a)-(EO)_(b)—R₁, wherein a is the average number-average molecularweight (MW_(PEI)) of the polyalkyleneimine core of the alkoxylatedpolyalkyleneimine and is in the range of from 100 to 100,000 Daltons,wherein b is the average degree of ethoxylation in said one or more sidechains of the alkoxylated polyalkyleneimine and is in the range of from5 to 40, and wherein R₁ is independently selected from the groupconsisting of hydrogen, C₁-C₄ alkyls, and combinations thereof.

Other suitable alkoxylated polyalkyleneimine incldue those wherein saidalkoxylated polyalkyleneimine has a polyalkyleneimine core with one ormore side chains bonded to at least one nitrogen atom in thepolyalkyleneimine core, wherein the alkoxylated polyalkyleneimine has anempirical formula (II) of (PEI)_(o)-(EO)_(m)(PO)_(n)—R₂ or(PEI)_(o)—(PO)_(n)(EO)_(m)—R₂, wherein o is the average number-averagemolecular weight (MW_(PEI)) of the polyalkyleneimine core of thealkoxylated polyalkyleneimine and is in the range of from 100 to 100,000Daltons, wherein m is the average degree of ethoxylation in said one ormore side chains of the alkoxylated polyalkyleneimine which ranges from10 to 50, wherein n is the average degree of propoxylation in said oneor more side chains of the alkoxylated polyalkyleneimine which rangesfrom 1 to 50, and wherein R₂ is independently selected from the groupconsisting of hydrogen, C₁-C₄ alkyls, and combinations thereof.

Amphiphilic graft co-polymer: Amphiphilic granft copolymer may also beused according to the invention. Especially useful polymers includethose comprising (i) polyethyelene glycol backbone; and (ii) and atleast one pendant moiety selected from polyvinyl acetate, polyvinylalcohol and mixtures thereof are also useful in thee rpessenttinvention. Suitable polyethylene glycol polymers include random graftco-polymers comprising: (i) hydrophilic backbone comprising polyethyleneglycol; and (ii) hydrophobic side chain(s) selected from the groupconsisting of: C₄-C₂₅ alkyl group, polypropylene, polybutylene, vinylester of a saturated C₁-C₆ mono-carboxylic acid, C₁-C₆ alkyl ester ofacrylic or methacrylic acid, and mixtures thereof. Suitable polyethyleneglycol polymers have a polyethylene glycol backbone with random graftedpolyvinyl acetate side chains. The average molecular weight of thepolyethylene glycol backbone can be in the range of from 2,000 Da to20,000 Da, or from 4,000 Da to 8,000 Da. The molecular weight ratio ofthe polyethylene glycol backbone to the polyvinyl acetate side chainscan be in the range of from 1:1 to 1:5, or from 1:1.2 to 1:2. Theaverage number of graft sites per ethylene oxide units can be less than1, or less than 0.8, the average number of graft sites per ethyleneoxide units can be in the range of from 0.5 to 0.9, or the averagenumber of graft sites per ethylene oxide units can be in the range offrom 0.1 to 0.5, or from 0.2 to 0.4. A suitable polyethylene glycolpolymer is Sokalan HP22. Suitable polyethylene glycol polymers aredescribed in WO08/007320.

Cellulosic polymer: Cellulosic polymers may be used according to theinvention. Suitable cellulosic polymers are selected from alkylcellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkylcarboxyalkyl cellulose, sulphoalkyl cellulose, more preferably selectedfrom carboxymethyl cellulose, methyl cellulose, methyl hydroxyethylcellulose, methyl carboxymethyl cellulose, and mixures thereof.

Suitable carboxymethyl celluloses have a degree of carboxymethylsubstitution from 0.5 to 0.9 and a molecular weight from 100,000 Da to300,000 Da.

Suitable carboxymethyl celluloses have a degree of substitution greaterthan 0.65 and a degree of blockiness greater than 0.45, e.g. asdescribed in WO09/154933.

The consumer products of the present invention may also include one ormore cellulosic polymers including those selected from alkyl cellulose,alkylalkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkylcellulose. In one aspect, the cellulosic polymers are selected from thegroup comprising carboxymethyl cellulose, methyl cellulose, methylhydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixturesthereof. In one aspect, the carboxymethyl cellulose has a degree ofcarboxymethyl substitution from 0.5 to 0.9 and a molecular weight from100,000 Da to 300,000 Da. Examples of carboxymethylcellulose polymersare Carboxymethyl cellulose commercially sold by CPKelko as Finnfix®GDA,hydrophobically modified carboxymethyl cellulose, for example the alkylketene dimer derivative of carboxymethylcellulose sold commercially byCPKelco as Finnfix®SH1, or the blocky carboxymethylcellulose soldcommercially by CPKelco as Finnfix®V.

Cationic Polymers: Cationic polymers may also be used according to theinvention. Suitable cationic polymers will have cationic chargedensities of at least 0.5 meq/gm, in another embodiment at least 0.9meq/gm, in another embodiment at least 1.2 meq/gm, in yet anotherembodiment at least 1.5 meq/gm, but in one embodiment also less than 7meq/gm, and in another embodiment less than 5 meq/gm, at the pH ofintended use of the composition, which pH will generally range from pH 3to pH 9, in one embodiment between pH 4 and pH 8. Herein, “cationiccharge density” of a polymer refers to the ratio of the number ofpositive charges on the polymer to the molecular weight of the polymer.The average molecular weight of such suitable cationic polymers willgenerally be between 10,000 and 10 million, in one embodiment between50,000 and 5 million, and in another embodiment between 100,000 and 3million.

Suitable cationic polymers for use in the compositions of the presentinvention contain cationic nitrogen-containing moieties such asquaternary ammonium or cationic protonated amino moieties. Any anioniccounterions can be used in association with the cationic polymers solong as the polymers remain soluble in water, in the composition, or ina coacervate phase of the composition, and so long as the counterionsare physically and chemically compatible with the essential componentsof the composition or do not otherwise unduly impair productperformance, stability or aesthetics. Nonlimiting examples of suchcounterions include halides (e.g., chloride, fluoride, bromide, iodide),sulfate and methylsulfate.

Nonlimiting examples of such polymers are described in the CTFA CosmeticIngredient Dictionary, 3rd edition, edited by Estrin, Crosley, andHaynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc.,Washington, D.C. (1982)).

Especially useful cationic polymers which may be used according to theinvention include wherein said cationic polymer comprises a polymerselected from the group consisting of cationic celluloses, cationicguars, poly(acrylamide-co-diallyldimethylammonium chloride),poly(acrylamide-co-diallyldimethylammonium chloride-co-acrylic acid),poly(acrylamide-co-methacryloamidopropyl-pentamethyl-1,3-propylene-2-ol-ammoniumdichloride), poly(acrylamide-co-N,N-dimethylaminoethyl acrylate) and itsquaternized derivatives, poly(acrylamide-co-N,N-dimethylaminoethylmethacrylate) and its quaternized derivatives,poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride),poly(acrylamide-methacrylamidopropyltrimethyl ammoniumchloride-co-acrylic acid), poly(diallyldimethyl ammonium chloride),poly(diallyldimethylammonium chloride-co-acrylic acid), poly(ethylmethacrylate-co-oleyl methacrylate-co-diethylaminoethyl methacrylate)and its quaternized derivatives, poly(ethylmethacrylate-co-dimethylaminoethyl methacrylate) and its quaternizedderivatives,poly(hydroxpropylacrylate-co-methacrylamidopropyltrimethylammoniumchloride) and its quaternized derivatives,poly(hydroxyethylacrylate-co-dimethyl aminoethyl methacrylate) and itsquaternized derivatives, poly(methylacrylamide-co-dimethylaminoethylacrylate) and its quaternized derivatives,poly(methacrylate-co-methacrylamidopropyltrimethyl ammonium chloride),poly(vinylformamide-co-acrylic acid-co-diallyldimethylammoniumchloride), poly(vinylformamide-co-diallyldimethylammonium chloride),poly(vinylpyrrolidone-co-acrylamide-co-vinyl imidazole) and itsquaternized derivatives, poly(vinylpyrrolidone-co-dimethylaminoethylmethacrylate) and its quaternized derivatives,poly(vinylpyrrolidone-co-methacrylamide-co-vinyl imidazole) and itsquaternized derivatives, poly(vinylpyrrolidone-co-vinyl imidazole) andits quaternized derivatives, polyethyleneimine and including itsquaternized derivatives, and mixtures thereof

Other suitable cationic polymers for use in the composition includepolysaccharide polymers, cationic guar gum derivatives, quaternarynitrogen-containing cellulose ethers, synthetic polymers, copolymers ofetherified cellulose, guar and starch. When used, the cationic polymersherein are either soluble in the composition or are soluble in a complexcoacervate phase in the composition formed by the cationic polymer andthe anionic, amphoteric and/or zwitterionic surfactant componentdescribed hereinbefore. Complex coacervates of the cationic polymer canalso be formed with other charged materials in the composition.

Suitable cationic polymers are described in U.S. Pat. Nos. 3,962,418;3,958,581; and U.S. Publication No. 2007/0207109A1.

Dye Transfer Inhibitor (DTI). The composition may comprise one or moredye transfer inhibiting agents. In one embodiment of the invention theinventors have surprisingly found that compositions comprising polymericdye transfer inhibiting agents in addition to the specified dye giveimproved performance. This is surprising because these polymers preventdye deposition. Suitable dye transfer inhibitors include, but are notlimited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.Suitable examples include PVP-K15, PVP-K30, ChromaBond S-400, ChromaBondS-403E and Chromabond S-100 from Ashland Aqualon, and Sokalan HP165,Sokalan HP50, Sokalan HP53, Sokalan HP59, Sokalan® HP 56K, Sokalan® HP66 from BASF. The dye control agent may be selected from (i) asulfonated phenol/formaldehyde polymer; (ii) a urea derivative; (iii)polymers of ethylenically unsaturated monomers, where the polymers aremolecularly imprinted with dye; (iv) fibers consisting ofwater-insoluble polyamide, wherein the fibers have an average diameterof not more than about 2 m; (v) a polymer obtainable from polymerizingbenzoxazine monomer compounds; and (vi) combinations thereof. Othersuitable DTIs are as described in WO2012/004134. When present in asubject composition, the dye transfer inhibiting agents may be presentat levels from about 0.0001% to about 10%, from about 0.01% to about 5%or even from about 0.1% to about 3% by weight of the composition.

Other water soluble polymers: Examples of water soluble polymers includebut are not limited to polyvinyl alcohols (PVA), modified PVAs;polyvinyl pyrrolidone; PVA copolymers such as PVA/polyvinyl pyrrolidoneand PVA/polyvinyl amine; partially hydrolyzed polyvinyl acetate;polyalkylene oxides such as polyethylene oxide; polyethylene glycols;acrylamide; acrylic acid; cellulose, alkyl cellulosics such as methylcellulose, ethyl cellulose and propyl cellulose; cellulose ethers;cellulose esters; cellulose amides; polyvinyl acetates; polycarboxylicacids and salts; polyaminoacids or peptides; polyamides; polyacrylamide;copolymers of maleic/acrylic acids; polysaccharides including starch,modified starch; gelatin; alginates; xyloglucans, other hemicellulosicpolysaccharides including xylan, glucuronoxylan, arabinoxylan, mannan,glucomannan and galactoglucomannan; and natural gums such as pectin,xanthan, and carrageenan, locus bean, arabic, tragacanth; andcombinations thereof

Non-limiting examples of amines include, but are not limited to,etheramines, cyclic amines, polyamines, oligoamines (e.g., triamines,diamines, pentamines, tetraamines), or combinations thereof. Thecompositions described herein may comprise an amine selected from thegroup consisting of oligoamines, etheramines, cyclic amines, andcombinations thereof. In some aspects, the amine is not an alkanolamine.In some aspects, the amine is not a polyalkyleneimine.

Examples of suitable oligoamines include tetraethylenepentamine,triethylenetetraamine, diethylenetriamine, and mixtures thereof

Etheramines: The cleaning compositions described herein may contain anetheramine. The cleaning compositions may contain from about 0.1% toabout 10%, or from about 0.2% to about 5%, or from about 0.5% to about4%, by weight of the composition, of an etheramine.

The etheramines of the present disclosure may have a weight averagemolecular weight of less than about grams/mole 1000 grams/mole, or fromabout 100 to about 800 grams/mole, or from about 200 to about 450grams/mole, or from about 290 to about 1000 grams/mole, or from about290 to about 900 grams/mole, or from about 300 to about 700 grams/mole,or from about 300 to about 450 grams/mole. The etheramines of thepresent invention may have a weight average molecular weight of fromabout 150, or from about 200, or from about 350, or from about 500grams/mole, to about 1000, or to about 900, or to about 800 grams/mole.

Alkoxylated phenol compound: The cleaning compositions of the presentdisclosure may include an alkoxylated phenol compound. The alkoxylatedphenol compound may be selected from the group consisting of analkoxylated polyaryl phenol compound, an alkoxylated polyalkyl phenolcompound, and mixtures thereof. The alkoxylated phenol compound may bean alkoxylated polyaryl phenol compound. The alkoxylated phenol compoundmay be an alkoxylated polyalkyl phenol compound.

The alkoxylated phenol compound may be present in the cleaningcomposition at a level of from about 0.2% to about 10%, or from about0.5% to about 5%, by weight of the cleaning composition.

The alkoxylated phenol compound may have a weight average molecularweight between 280 and 2880.

Enzymes. Preferably the composition comprises one or more enzymes.Preferred enzymes provide cleaning performance and/or fabric carebenefits. Examples of suitable enzymes include, but are not limited to,hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases,phospholipases, esterases, cutinases, pectinases, mannanases, pectatelyases, keratinases, reductases, oxidases, phenoloxidases,lipoxygenases, ligninases, pullulanases, tannases, pentosanases,malanases, 1-glucanases, arabinosidases, hyaluronidase, chondroitinase,laccase, and amylases, or mixtures thereof. A typical combination is anenzyme cocktail that may comprise, for example, a protease and lipase inconjunction with amylase. When present in the composition, theaforementioned additional enzymes may be present at levels from about0.00001% to about 2%, from about 0.0001% to about 1% or even from about0.001% to about 0.5% enzyme protein by weight of the composition.

Proteases. Preferably the composition comprises one or more proteases.Suitable proteases include metalloproteases and serine proteases,including neutral or alkaline microbial serine proteases, such assubtilisins (EC 3.4.21.62). Suitable proteases include those of animal,vegetable or microbial origin. In one aspect, such suitable protease maybe of microbial origin. The suitable proteases include chemically orgenetically modified mutants of the aforementioned suitable proteases.In one aspect, the suitable protease may be a serine protease, such asan alkaline microbial protease or/and a trypsin-type protease. Examplesof suitable neutral or alkaline proteases include:

(a) subtilisins (EC 3.4.21.62), including those derived from Bacillus,such as Bacillus lentus, B. alkalophilus, B. subtilis, B.amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described inU.S. Pat. No. 6,312,936 B1, U.S. Pat. Nos. 5,679,630, 4,760,025,7,262,042 and WO09/021867.

(b) trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g.,of porcine or bovine origin), including the Fusarium protease describedin WO 89/06270 and the chymotrypsin proteases derived from Cellumonasdescribed in WO 05/052161 and WO 05/052146.

(c) metalloproteases, including those derived from Bacillusamyloliquefaciens described in WO 07/044993A2.

Preferred proteases include those derived from Bacillus gibsonii orBacillus Lentus.

Suitable commercially available protease enzymes include those soldunder the trade names Alcalase®, Savinase®, Primase®, Durazym®,Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®,Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark),those sold under the tradename Maxatase®, Maxacal®, Maxapem®,Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®,Excellase® and Purafect OXP® by Genencor International, those sold underthe tradename Opticlean® and Optimase® by Solvay Enzymes, thoseavailable from Henkel/Kemira, namely BLAP (sequence shown in FIG. 29 ofU.S. Pat. No. 5,352,604 with the following mutations S99D+S101R+S103A+V104I+G159S, hereinafter referred to as BLAP), BLAP R (BLAP withS3T+V4I+V199M+V205I+L217D), BLAP X (BLAP with S3T+V4I+V205I) and BLAPF49 (BLAP with S3T+V4I+A194P+V199M+V205I+L217D)—all from Henkel/Kemira;and KAP (Bacillus alkalophilus subtilisin with mutationsA230V+S256G+S259N) from Kao.

Amylases. Preferably the composition may comprise an amylase. Suitablealpha-amylases include those of bacterial or fungal origin. Chemicallyor genetically modified mutants (variants) are included. A preferredalkaline alpha-amylase is derived from a strain of Bacillus, such asBacillus licheniformis, Bacillus amyloliquefaciens, Bacillusstearothermophilus, Bacillus subtilis, or other Bacillus sp., such asBacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (U.S. Pat. No.7,153,818) DSM 12368, DSMZ no. 12649, KSM AP1378 (WO 97/00324), KSM K36or KSM K38 (EP 1,022,334). Preferred amylases include:

(a) the variants described in WO 94/02597, WO 94/18314, WO96/23874 andWO 97/43424, especially the variants with substitutions in one or moreof the following positions versus the enzyme listed as SEQ ID No. 2 inWO 96/23874: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190,197, 202, 208, 209, 243, 264, 304, 305, 391, 408, and 444.

(b) the variants described in U.S. Pat. No. 5,856,164 and WO99/23211, WO96/23873, WO00/60060 and WO 06/002643, especially the variants with oneor more substitutions in the following positions versus the AA560 enzymelisted as SEQ ID No. 12 in WO 06/002643:

26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186,193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298,299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383,419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484,preferably that also contain the deletions of D183* and G184*.

(c) variants exhibiting at least 90% identity with SEQ ID No. 4 inWO06/002643, the wild-type enzyme from Bacillus SP722, especiallyvariants with deletions in the 183 and 184 positions and variantsdescribed in WO 00/60060, which is incorporated herein by reference.

(d) variants exhibiting at least 95% identity with the wild-type enzymefrom Bacillus sp. 707 (SEQ ID NO:7 in U.S. Pat. No. 6,093,562),especially those comprising one or more of the following mutations M202,M208, S255, R172, and/or M261. Preferably said amylase comprises one ormore of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N and/orR172Q. Particularly preferred are those comprising the M202L or M202Tmutations.

(e) variants described in WO 09/149130, preferably those exhibiting atleast 90% identity with SEQ ID NO: 1 or SEQ ID NO:2 in WO 09/149130, thewild-type enzyme from Geobacillus Stearophermophilus or a truncatedversion thereof.

Suitable commercially available alpha-amylases include DURAMYL®,LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®,STAINZYME®, STAINZYME PLUS®, FUNGAMYL® and BAN® (Novozymes A/S,Bagsvaerd, Denmark), KEMZYM® AT 9000 Biozym Biotech Trading GmbHWehlistrasse 27b A-1200 Wien Austria, RAPIDASE®, PURASTAR®, ENZYSIZE®,OPTISIZE HT PLUS®, POWERASE® and PURASTAR OXAM® (Genencor InternationalInc., Palo Alto, Calif.) and KAM® (Kao, 14-10 Nihonbashi Kayabacho,1-chome, Chuo-ku Tokyo 103-8210, Japan). In one aspect, suitableamylases include NATALASE®, STAINZYME® and STAINZYME PLUS® and mixturesthereof.

Lipases. Preferably the invention comprises one or more lipases,including “first cycle lipases” such as those described in U.S. Pat. No.6,939,702 B1 and US PA 2009/0217464. Preferred lipases are first-washlipases. In one embodiment of the invention the composition comprises afirst wash lipase. First wash lipases includes a lipase which is apolypeptide having an amino acid sequence which: (a) has at least 90%identity with the wild-type lipase derived from Humicola lanuginosastrain DSM 4109; (b) compared to said wild-type lipase, comprises asubstitution of an electrically neutral or negatively charged amino acidat the surface of the three-dimensional structure within 15A of E1 orQ249 with a positively charged amino acid; and (c) comprises a peptideaddition at the C-terminal; and/or (d) comprises a peptide addition atthe N-terminal and/or (e) meets the following limitations: i) comprisesa negative amino acid in position E210 of said wild-type lipase; ii)comprises a negatively charged amino acid in the region corresponding topositions 90-101 of said wild-type lipase; and iii) comprises a neutralor negative amino acid at a position corresponding to N94 or saidwild-type lipase and/or has a negative or neutral net electric charge inthe region corresponding to positions 90-101 of said wild-type lipase.Preferred arevariants of the wild-type lipase from Thermomyceslanuginosus comprising one or more of the T231R and N233R mutations. Thewild-type sequence is the 269 amino acids (amino acids 23-291) of theSwissprot accession number Swiss-Prot 059952 (derived from Thermomyceslanuginosus (Humicola lanuginosa)). Preferred lipases would includethose sold under the tradenames Lipex® and Lipolex® and Lipoclean®.

Endoglucanases. Other preferred enzymes include microbial-derivedendoglucanases exhibiting endo-beta-1,4-glucanase activity (E.C.3.2.1.4), including a bacterial polypeptide endogenous to a member ofthe genus Bacillus which has a sequence of at least 90%, 94%, 97% andeven 99% identity to the amino acid sequence SEQ ID NO:2 in U.S. Pat.No. 7,141,403B2) and mixtures thereof. Suitable endoglucanases are soldunder the tradenames Celluclean® and Whitezyme® (Novozymes A/S,Bagsvaerd, Denmark).

Pectate Lyases. Other preferred enzymes include pectate lyases soldunder the tradenames Pectawash®, Pectaway®, Xpect® and mannanases soldunder the tradenames Mannaway® (all from Novozymes A/S, Bagsvaerd,Denmark), and Purabrite® (Genencor International Inc., Palo Alto,Calif.).

Nuclease enzyme. The composition may comprise a nuclease enzyme. Thenuclease enzyme is an enzyme capable of cleaving the phosphodiesterbonds between the nucleotide sub-units of nucleic acids. The nucleaseenzyme herein is preferably a deoxyribonuclease or ribonuclease enzymeor a functional fragment thereof. By functional fragment or part ismeant the portion of the nuclease enzyme that catalyzes the cleavage ofphosphodiester linkages in the DNA backbone and so is a region of saidnuclease protein that retains catalytic activity. Thus it includestruncated, but functional versions, of the enzyme and/or variants and/orderivatives and/or homologues whose functionality is maintained.

Preferably the nuclease enzyme is a deoxyribonuclease, preferablyselected from any of the classes E.C. 3.1.21.x, where x=1, 2, 3, 4, 5,6, 7, 8 or 9, E.C. 3.1.22.y where y=1, 2, 4 or 5, E.C. 3.1.30.z wherez=1 or 2, E.C. 3.1.31.1 and mixtures thereof.

Bleaching Agents. It may be preferred for the composition to compriseone or more bleaching agents. Suitable bleaching agents other thanbleaching catalysts include photobleaches, bleach activators, hydrogenperoxide, sources of hydrogen peroxide, pre-formed peracids and mixturesthereof. In general, when a bleaching agent is used, the compositions ofthe present invention may comprise from about 0.1% to about 50% or evenfrom about 0.1% to about 25% bleaching agent or mixtures of bleachingagents by weight of the subject composition. Examples of suitablebleaching agents include:

(1) photobleaches for example sulfonated zinc phthalocyanine sulfonatedaluminium phthalocyanines, xanthene dyes, thioxanthones, and mixturesthereof;

(2) pre-formed peracids: Suitable preformed peracids include, but arenot limited to compounds selected from the group consisting ofpre-formed peroxyacids or salts thereof typically a percarboxylic acidsand salts, percarbonic acids and salts, perimidic acids and salts,peroxymonosulfuric acids and salts, for example, Oxone®, and mixturesthereof.

Particularly preferred peroxyacids are phthalimido-peroxy-alkanoicacids, in particular ε-phthalimido peroxy hexanoic acid (PAP).Preferably, the peroxyacid or salt thereof has a melting point in therange of from 30° C. to 60° C.

(3) sources of hydrogen peroxide, for example, inorganic perhydratesalts, including alkali metal salts such as sodium salts of perborate(usually mono- or tetra-hydrate), percarbonate, persulphate,perphosphate, persilicate salts and mixtures thereof. When employed,inorganic perhydrate salts are typically present in amounts of from 0.05to 40 wt %, or 1 to 30 wt % of the overall fabric and home care productand are typically incorporated into such fabric and home care productsas a crystalline solid that may be coated. Suitable coatings include,inorganic salts such as alkali metal silicate, carbonate or borate saltsor mixtures thereof, or organic materials such as water-soluble ordispersible polymers, waxes, oils or fatty soaps; and

(4) bleach activators having R—(C═O)-L wherein R is an alkyl group,optionally branched, having, when the bleach activator is hydrophobic,from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when thebleach activator is hydrophilic, less than 6 carbon atoms or even lessthan 4 carbon atoms; and L is leaving group. Examples of suitableleaving groups are benzoic acid and derivatives thereof—especiallybenzene sulphonate. Suitable bleach activators include dodecanoyloxybenzene sulphonate, decanoyl oxybenzene sulphonate, decanoyloxybenzoic acid or salts thereof, 3,5,5-trimethyl hexanoyloxybenzenesulphonate, tetraacetyl ethylene diamine (TAED) and nonanoyloxybenzenesulphonate (NOBS).

(5) Bleach Catalysts. The compositions of the present invention may alsoinclude one or more bleach catalysts capable of accepting an oxygen atomfrom a peroxyacid and/or salt thereof, and transferring the oxygen atomto an oxidizeable substrate. Suitable bleach catalysts include, but arenot limited to: iminium cations and polyions; iminium zwitterions;modified amines; modified amine oxides; N-sulphonyl imines; N-phosphonylimines; N-acyl imines; thiadiazole dioxides; perfluoroimines; cyclicsugar ketones and alpha amino-ketones and mixtures thereof. Oneparticularly preferred catalyst is acyl hydrazone type such as4-(2-(2-((2-hydroxyphenylmethyl)methylene)-hydrazinyl)-2-oxoethyl)-4-methylchloride.

(6) The composition may preferably comprise catalytic metal complexes.One preferred type of metal-containing bleach catalyst is a catalystsystem comprising a transition metal cation of defined bleach catalyticactivity, such as copper, iron, titanium, ruthenium, tungsten,molybdenum, or manganese cations.

If desired, the compositions herein can be catalyzed by means of amanganese compound. Such compounds and levels of use are well known inthe art and include, for example, the manganese-based catalystsdisclosed in U.S. Pat. No. 5,576,282. In some embodiments, an additionalsource of oxidant in the composition is not present, molecular oxygenfrom air providing the oxidative source.

Cobalt bleach catalysts useful herein are known, and are described, forexample, in U.S. Pat. Nos. 5,597,936; 5,595,967.

When present, the source of hydrogen peroxide/peracid and/or bleachactivator is generally present in the composition in an amount of fromabout 0.1 to about 60 wt %, from about 0.5 to about 40 wt % or even fromabout 0.6 to about 10 wt % based on the fabric and home care product.One or more hydrophobic peracids or precursors thereof may be used incombination with one or more hydrophilic peracid or precursor thereof.

Typically hydrogen peroxide source and bleach activator will beincorporated together. The amounts of hydrogen peroxide source andperacid or bleach activator may be selected such that the molar ratio ofavailable oxygen (from the peroxide source) to peracid is from 1:1 to35:1, or even 2:1 to 10:1. If formulated into a liquid detergent, theperoxide source and activator may be formulated at low pH, typically 3-5together with a pH jump system such as borate/sorbitol.

The laundry care compositions of the present invention may be especiallyused in chlorinated water such as typically found in most domestic watersupplies. Alternatively the leuco comprising systems may be used inconjunction with other sources of bleaching such as electrolysis and maybe used in an autodosed system.

Builders. Preferably the composition may comprise one or more buildersor a builder system. When a builder is used, the composition of theinvention will typically comprise at least 1%, from 2% to 60% builder.It may be preferred that the composition comprises low levels ofphosphate salt and/or zeolite, for example from 1 to 10 or 5 wt %. Thecomposition may even be substantially free of strong builder;substantially free of strong builder means “no deliberately added”zeolite and/or phosphate. Typical zeolite builders include zeolite A,zeolite P and zeolite MAP. A typical phosphate builder is sodiumtri-polyphosphate.

Chelating Agent. Preferably the composition comprises chelating agentsand/or crystal growth inhibitor. Suitable molecules include copper, ironand/or manganese chelating agents and mixtures thereof. Suitablemolecules include hydroxamic acids, aminocarboxylates,aminophosphonates, succinates, salts thereof, and mixtures thereof.Non-limiting examples of suitable chelants for use herein includeethylenediaminetetracetates, N-(hydroxyethyl)ethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates,ethanoldiglycines, ethylenediaminetetrakis (methylenephosphonates),diethylenetriamine penta(methylene phosphonic acid) (DTPMP),ethylenediamine disuccinate (EDDS), hydroxyethanedimethylenephosphonicacid (HEDP), methylglycinediacetic acid (MGDA),diethylenetriaminepentaacetic acid (DTPA), salts thereof, and mixturesthereof. Other nonlimiting examples of chelants of use in the presentinvention are found in U.S. Pat. Nos. 7,445,644, 7,585,376 and2009/0176684A1. Other suitable chelating agents for use herein are thecommercial DEQUEST series, and chelants from Monsanto, DuPont, andNalco, Inc. Yet other suitable chelants include the pyridinyl N Oxidetype

Fluorescent Brightener. Preferably the composition comprises one or morefluorescent brightener. Commercial optical brighteners which may beuseful in the present invention can be classified into subgroups, whichinclude, but are not limited to, derivatives of stilbene, pyrazoline,coumarin, carboxylic acid, methinecyanines,dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ringheterocycles, and other miscellaneous agents. Particularly preferredbrighteners are selected from: sodium 2(4-styryl-3-sulfophenyl)-2H-napthol [1,2-d] triazole, disodium4,4′-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino1,3,5-triazin-2-yl)] amino}stilbene-2-2-disulfonate, disodium 4,4′-bis{[(4-anilino-6-morpholino-1, 3, 5-triazin-2-yl)] amino}stilbene-2-2′ disulfonate, and disodium 4,4′-bis (2-sulfostyryl)biphenyl. Other examples of such brighteners are disclosed in “TheProduction and Application of Fluorescent Brightening Agents”, M.Zahradnik, Published by John Wiley & Sons, New York (1982). Specificnonlimiting examples of optical brighteners which are useful in thepresent compositions are those identified in U.S. Pat. Nos. 4,790,856and 3,646,015.

A preferred brightener has the structure below:

Suitable fluorescent brightener levels include lower levels of fromabout 0.01, from about 0.05, from about 0.1 or even from about 0.2 wt %to upper levels of 0.5 or even 0.75 wt %.

In one aspect the brightener may be loaded onto a clay to form aparticle.

Preferred brighteners are totally or predominantly (typically at least50 wt %, at least 75 wt %, at least 90 wt %, at least 99 wt %), inalpha-crystalline form. A highly preferred brightener comprises C.I.fluorescent brightener 260, preferably having the following structure:

This can be particularly useful as it dissolves well in cold water, forexample below 30° C. or 25° C. or even 20° C.

Enzyme Stabilizers. The composition may preferably comprise enzymestabilizers. Any conventional enzyme stabilizer may be used, for exampleby the presence of water-soluble sources of calcium and/or magnesiumions in the finished fabric and home care products that provide suchions to the enzymes. In case of aqueous compositions comprisingprotease, a reversible protease inhibitor, such as a boron compoundincluding borate, or preferably 4-formyl phenylboronic acid,phenylboronic acid and derivatives thereof, or compounds such as calciumformate, sodium formate and 1,2-propane diol can be added to furtherimprove stability.

Solvent System. The solvent system in the present compositions can be asolvent system containing water alone or mixtures of organic solventseither without or preferably with water.

Organic Solvents

The compositions may optionally comprise an organic solvent. Suitableorganic solvents include C₄₋₁₄ ethers and diethers, glycols, alkoxylatedglycols, C₆-C₁₆ glycol ethers, alkoxylated aromatic alcohols, aromaticalcohols, aliphatic branched alcohols, alkoxylated aliphatic branchedalcohols, alkoxylated linear C₁-C₅ alcohols, linear C₁-C₅ alcohols,amines, C₈-C₁₄ alkyl and cycloalkyl hydrocarbons and halohydrocarbons,and mixtures thereof. Preferred organic solvents include1,2-propanediol, 2,3 butane diol, ethanol, glycerol, ethoxylatedglycerol, dipropylene glycol, methyl propane diol and mixtures thereof.Other lower alcohols, C₁-C₄ alkanolamines such as monoethanolamine andtriethanolamine, can also be used. Solvent systems can be absent, forexample from anhydrous solid embodiments of the invention, but moretypically are present at levels in the range of from about 0.1% to about98%, preferably at least about 1% to about 50%, more usually from about5% to about 25%, alternatively from about 1% to about 10% by weight ofthe liquid detergent composition of said organic solvent. These organicsolvents may be used in conjunction with water, or they may be usedwithout water

Structured Liquids: In some embodiments of the invention, thecomposition is in the form of a structured liquid. Such structuredliquids can either be internally structured, whereby the structure isformed by primary ingredients (e.g. surfactant material) and/orexternally structured by providing a three dimensional matrix structureusing secondary ingredients (e.g. polymers, clay and/or silicatematerial), for use e.g. as thickeners. The composition may comprise astructurant, preferably from 0.01 wt % to 5 wt %, from 0.1 wt % to 2.0wt % structurant. Examples of suitable structurants are given inUS2006/0205631A1, US2005/0203213A1, U.S. Pat. Nos. 7,294,611, 6,855,680.The structurant is typically selected from the group consisting ofdiglycerides and triglycerides, ethylene glycol distearate,microcrystalline cellulose, cellulose-based materials, microfibercellulose, hydrophobically modified alkali-swellable emulsions such asPolygel W30 (3VSigma), biopolymers, xanthan gum, gellan gum,hydrogenated castor oil, derivatives of hydrogenated castor oil such asnon-ethoxylated derivatives thereof and mixtures thereof, in particular,those selected from the group of hydrogenated castor oil, derivatives ofhydrogenated castor oil, microfibullar cellulose, hydroxyfunctionalcrystalline materials, long chain fatty alcohols, 12-hydroxystearicacids, clays and mixtures thereof. One preferred structurant isdescribed in U.S. Pat. No. 6,855,680 which defines suitablehydroxyfunctional crystalline materials in detail. Preferred ishydrogenated castor oil. Some structurants have a thread-likestructuring system having a range of aspect ratios. Another preferredstructurant is based on cellulose and may be derived from a number ofsources including biomass, wood pulp, citrus fibers and the like.

The composition of the present invention may comprise a high meltingpoint fatty compound. The high melting point fatty compound usefulherein has a melting point of 25° C. or higher, and is selected from thegroup consisting of fatty alcohols, fatty acids, fatty alcoholderivatives, fatty acid derivatives, and mixtures thereof. Suchcompounds of low melting point are not intended to be included in thissection. Non-limiting examples of the high melting point compounds arefound in International Cosmetic Ingredient Dictionary, Fifth Edition,1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992. Whenpresent, the high melting point fatty compound is preferably included inthe composition at a level of from 0.1% to 40%, preferably from 1% to30%, more preferably from 1.5% to 16% by weight of the composition, from1.5% to 8% in view of providing improved conditioning benefits such asslippery feel during the application to wet hair, softness andmoisturized feel on dry hair.

Cationic Polymer. The compositions of the present invention may containa cationic polymer. Concentrations of the cationic polymer in thecomposition typically range from 0.05% to 3%, in another embodiment from0.075% to 2.0%, and in yet another embodiment from 0.1% to 1.0%.Suitable cationic polymers will have cationic charge densities of atleast 0.5 meq/gm, in another embodiment at least 0.9 meq/gm, in anotherembodiment at least 1.2 meq/gm, in yet another embodiment at least 1.5meq/gm, but in one embodiment also less than 7 meq/gm, and in anotherembodiment less than 5 meq/gm, at the pH of intended use of thecomposition, which pH will generally range from pH 3 to pH 9, in oneembodiment between pH 4 and pH 8. Herein, “cationic charge density” of apolymer refers to the ratio of the number of positive charges on thepolymer to the molecular weight of the polymer. The average molecularweight of such suitable cationic polymers will generally be between10,000 and 10 million, in one embodiment between 50,000 and 5 million,and in another embodiment between 100,000 and 3 million.

Suitable cationic polymers for use in the compositions of the presentinvention contain cationic nitrogen-containing moieties such asquaternary ammonium or cationic protonated amino moieties. Any anioniccounterions can be used in association with the cationic polymers solong as the polymers remain soluble in water, in the composition, or ina coacervate phase of the composition, and so long as the counterionsare physically and chemically compatible with the essential componentsof the composition or do not otherwise unduly impair productperformance, stability or aesthetics. Nonlimiting examples of suchcounterions include halides (e.g., chloride, fluoride, bromide, iodide),sulfate and methylsulfate.

Nonlimiting examples of such polymers are described in the CTFA CosmeticIngredient Dictionary, 3rd edition, edited by Estrin, Crosley, andHaynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc.,Washington, D.C. (1982)).

Other suitable cationic polymers for use in the composition includepolysaccharide polymers, cationic guar gum derivatives, quaternarynitrogen-containing cellulose ethers, synthetic polymers, copolymers ofetherified cellulose, guar and starch. When used, the cationic polymersherein are either soluble in the composition or are soluble in a complexcoacervate phase in the composition formed by the cationic polymer andthe anionic, amphoteric and/or zwitterionic surfactant componentdescribed hereinbefore. Complex coacervates of the cationic polymer canalso be formed with other charged materials in the composition.

Suitable cationic polymers are described in U.S. Pat. Nos. 3,962,418;3,958,581; and U.S. Publication No. 2007/0207109A1.

Nonionic Polymer. The composition of the present invention may include anonionic polymer as a conditioning agent. Polyalkylene glycols having amolecular weight of more than 1000 are useful herein. Useful are thosehaving the following general formula:

wherein R⁹⁵ is selected from the group consisting of H, methyl, andmixtures thereof.

Conditioning agents, and in particular silicones, may be included in thecomposition. The conditioning agents useful in the compositions of thepresent invention typically comprise a water insoluble, waterdispersible, non-volatile, liquid that forms emulsified, liquidparticles. Suitable conditioning agents for use in the composition arethose conditioning agents characterized generally as silicones (e.g.,silicone oils, cationic silicones, silicone gums, high refractivesilicones, and silicone resins), organic conditioning oils (e.g.,hydrocarbon oils, polyolefins, and fatty esters) or combinationsthereof, or those conditioning agents which otherwise form liquid,dispersed particles in the aqueous surfactant matrix herein. Suchconditioning agents should be physically and chemically compatible withthe essential components of the composition, and should not otherwiseunduly impair product stability, aesthetics or performance.

The concentration of the conditioning agent in the composition should besufficient to provide the desired conditioning benefits. Suchconcentration can vary with the conditioning agent, the conditioningperformance desired, the average size of the conditioning agentparticles, the type and concentration of other components, and otherlike factors.

The concentration of the silicone conditioning agent typically rangesfrom about 0.01% to about 10%. Non-limiting examples of suitablesilicone conditioning agents, and optional suspending agents for thesilicone, are described in U.S. Reissue Pat. No. 34,584, U.S. Pat. Nos.5,104,646; 5,106,609; 4,152,416; 2,826,551; 3,964,500; 4,364,837;6,607,717; 6,482,969; 5,807,956; 5,981,681; 6,207,782; 7,465,439;7,041,767; 7,217,777; US Patent Application Nos. 2007/0286837A1;2005/0048549A1; 2007/0041929A1; British Pat. No. 849,433; German PatentNo. DE 10036533, which are all incorporated herein by reference;Chemistry and Technology of Silicones, New York: Academic Press (1968);General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54and SE 76; Silicon Compounds, Petrarch Systems, Inc. (1984); and inEncyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., pp204-308, John Wiley & Sons, Inc. (1989).

Organic Conditioning Oil. The compositions of the present invention mayalso comprise from about 0.05% to about 3% of at least one organicconditioning oil as the conditioning agent, either alone or incombination with other conditioning agents, such as the silicones(described herein). Suitable conditioning oils include hydrocarbon oils,polyolefins, and fatty esters. Hygiene Agent. The compositions of thepresent invention may also comprise components to deliver hygiene and/ormalodour benefits such as one or more of zinc ricinoleate, thymol,quaternary ammonium salts such as Bardac®, polyethylenimines (such asLupasol® from BASF) and zinc complexes thereof, silver and silvercompounds, especially those designed to slowly release Ag+ ornano-silver dispersions.

Probiotics. The composition may comprise probiotics, such as thosedescribed in WO2009/043709.

Suds Boosters. The composition may preferably comprise suds boosters ifhigh sudsing is desired. Suitable examples are the C₁₀-C₁₆ alkanolamidesor C₁₀-C₁₄ alkyl sulphates, which are preferably incorporated at 1%-10%levels. The C₁₀-C₁₄ monoethanol and diethanol amides illustrate atypical class of such suds boosters. Use of such suds boosters with highsudsing adjunct surfactants such as the amine oxides, betaines andsultaines noted above is also advantageous. If desired, water-solublemagnesium and/or calcium salts such as MgCl₂, MgSO₄, CaCl₂, CaSO₄ andthe like, can be added at levels of, typically, 0.1%-2%, to provideadditional suds and to enhance grease removal performance.

Suds Suppressor. Compounds for reducing or suppressing the formation ofsuds may be incorporated into the compositions of the present invention.Suds suppression can be of particular importance in the so-called “highconcentration cleaning process” as described in U.S. Pat. Nos. 4,489,455and 4,489,574, and in front-loading-style washing machines. A widevariety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). Examples ofsuds suppressors include monocarboxylic fatty acid and soluble saltstherein, high molecular weight hydrocarbons such as paraffin, fatty acidesters (e.g., fatty acid triglycerides), fatty acid esters of monovalentalcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point belowabout 100° C., silicone suds suppressors, and secondary alcohols.Particularly useful silicone suds suppressors are based on diphenylcontaining silicones.

Silicone suds suppressors are typically utilized in amounts up to 2.0%,by weight, of the detergent composition, although higher amounts may beused.

Pearlescent Agents. Pearlescent agents as described in WO2011/163457 maybe incorporated into the compositions of the invention.

The pearlescent agents can be crystalline or glassy solids, transparentor translucent compounds capable of reflecting and refracting light toproduce a pearlescent effect. Typically, the pearlescent agents arecrystalline particles insoluble in the composition in which they areincorporated. Preferably the pearlescent agents have the shape of thinplates or spheres. Particle size of the pearlescent agent is typicallybelow 200 microns, preferably below 100 microns, more preferably below50 microns. Inorganic pearlescent agents include aluminosilicates and/orborosilicates. Preferred are the aluminosilicates and/or borosilicateswhich have been treated to have a very high refractive index, preferablysilica, metal oxides, oxychloride coated aluminosilicate and/orborosilicates. More preferred inorganic pearlescent agent is mica, evenmore preferred titanium dioxide treated mica such as BASF MearlinSuperfine.

The compositions may comprise from 0.005% to 3.0% wt, preferably from0.01% to 1%, by weight of the composition of the 100% active pearlescentagents. The pearlescent agents may be organic or inorganic. Thecomposition can comprise organic and/or inorganic pearlescent agent.

Organic Pearlescent Agents:

When the composition comprises an organic pearlescent agent, it iscomprised at an active level of from 0.05% to 2.0% wt, preferably from0.1% to 1.0% by weight of the composition of the 100% active organicpearlescent agents. Suitable organic pearlescent agents includemonoester and/or diester of alkylene glycols such as ethylene glycoldistearate.

Inorganic Pearlescent Agents:

In another embodiment the composition might also comprise an inorganicpearlescent agent. When the composition comprises an inorganicpearlescent agent, it is comprised at an active level of from 0.005% to1.0% wt, preferably from 0.01% to 0.2% by weight of the composition ofthe 100% active inorganic pearlescent agents.

Suspension Particles

In one embodiment, the composition further comprises a plurality ofsuspension particles at a level of from about 0.01% to about 5% byweight, alternatively from about 0.05% to about 4% by weight,alternatively from about 0.1% to about 3% by weight. Examples ofsuitable suspension particles are provided in U.S. Pat. No. 7,169,741and U.S. Patent Publ. No. 2005/0203213, the disclosures of which areincorporated herein by reference. These suspended particles can comprisea liquid core or a solid core. Detailed description of these liquid coreand solid core particles, as well as description of preferred particlesize, particle shape, particle density, and particle burst strength aredescribed in U.S. patent application Ser. No. 12/370,714, the disclosureof which is incorporated herein by reference.

In one preferred embodiment, the particles may be any discrete andvisually distinguishable form of matter, including but not limiting to(deformable) beads, encapsulates, polymeric particles like plastic,metals (e.g. foil material, flakes, glitter), (interference) pigments,minerals (salts, rocks, pebbles, lava, glass/silica particles, talc),plant materials (e.g. pits or seeds, plant fibers, stalks, stems, leavesor roots), solid and liquid crystals, and the like. Different particleshapes are possible, ranging from spherical to tabular.

In one embodiment, the suspension particles may be gas or air bubbles.In this embodiment, the diameter of each bubble may be from about 50 toabout 2000 microns and may be present at a level of about 0.01 to about5% by volume of the composition alternatively from about 0.05% to about4% by volume of the composition, alternatively from about 0.1% to about3% by volume of the composition.

Opacifier

In one embodiment, the composition might also comprise an opacifier.

As the term is used herein, an “opacifier” is a substance added to amaterial in order to make the ensuing system opaque. In one preferredembodiment, the opacifier is Acusol, which is available from DowChemicals. Acusol opacifiers are provided in liquid form at a certain %solids level. As supplied, the pH of Acusol opacifiers ranges from 2.0to 5.0 and particle sizes range from 0.17 to 0.45 um. In one preferredembodiment, Acusol OP303B and 301 can be used.

In yet another embodiment, the opacifier may be an inorganic opacifier.Preferably, the inorganic opacifier can be TiO₂, ZnO, talc, CaCO₃, andcombination thereof. The composite opacifier-microsphere material isreadily formed with a preselected specific gravity, so that there islittle tendency for the material to separate.

Hydrotrope: The composition may optionally comprises a hydrotrope in aneffective amount, i.e. from about 0% to 15%, or about 1% to 10%, orabout 3% to about 6%, so that compositions are compatible in water.Suitable hydrotropes for use herein include anionic-type hydrotropes,particularly sodium, potassium, and ammonium xylene sulfonate, sodium,potassium and ammonium toluene sulfonate, sodium potassium and ammoniumcumene sulfonate, and mixtures thereof, as disclosed in U.S. Pat. No.3,915,903.

Anti-oxidant: The composition may optionally contain an anti-oxidantpresent in the composition from about 0.001 to about 2% by weight.Preferably the antioxidant is present at a concentration in the range0.01 to 0.08% by weight. Mixtures of anti-oxidants may be used.

Anti-oxidants are substances as described in Kirk-Othmer (Vol. 3, page424) and In Ullmann's Encyclopedia (Vol. 3, page 91).

One class of anti-oxidants used in the present invention is alkylatedphenols, having the general formula:

wherein R is C₁-C₂₂ linear or branched alkyl, preferably methyl orbranched C₃-C₆ alkyl, C₁-C₆ alkoxy, preferably methoxy; R₁ is a C₃-C₆branched alkyl, preferably tert-butyl; x is 1 or 2. Hindered phenoliccompounds are a preferred type of alkylated phenols having this formula.A preferred hindered phenolic compound of this type is2,6-di-tert-butyl-hydroxytoluene (BHT).

Furthermore, the anti-oxidant used in the composition may be selectedfrom the group consisting of α-, β-, γ-, δ-tocopherol, ethoxyquin,2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-tert-butyl hydroquinone,tert-butyl hydroxyanisole, lignosulphonic acid and salts thereof, andmixtures thereof. It is noted that ethoxyquin(1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline) is marketed under thename Raluquin™ by the company Raschig™.

Other types of anti-oxidants that may be used in the composition are6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox™) and1,2-benzisothiazoline-3-one (Proxel GXL™).

A further class of anti-oxidants which may be suitable for use in thecomposition is a benzofuran or benzopyran derivative having the formula:

wherein R₁ and R₂ are each independently alkyl or R₁ and R₂ can be takentogether to form a C₅-C₆ cyclic hydrocarbyl moiety; B is absent or CH₂;R₄ is C₁-C₆ alkyl; R_(s) is hydrogen or —C(O)R₃ wherein R₃ is hydrogenor C₁-C₉ alkyl; R₆ is C₁-C₆ alkyl; R₇ is hydrogen or C₁-C₆ alkyl; X is—CH₂OH, or —CH₂A wherein A is a nitrogen comprising unit, phenyl, orsubstituted phenyl. Preferred nitrogen comprising A units include amino,pyrrolidino, piperidino, morpholino, piperazino, and mixtures thereof.

Anti-oxidants such as tocopherol sorbate, butylated hydroxyl benxoicacids and their salts, gallic acid and its alkyl esters, uric acid andits salts, sorbic acid and its salts, and dihydroxyfumaric acid and itssalts may also be used. In one aspect, the most preferred types ofanti-oxidant for use in the composition are2,6-di-tert-butylhydroxytoluene (BHT), □-, □-, □-, □□tocopherol,1,2-benzisothiazoline-3-one (Proxel GXL™) and mixtures thereof.

Packaging. Any conventional packaging may be used and the packaging maybe fully or partially transparent so that the consumer can see the colorof the laundry care composition which may be provided or contributed toby the color of the dyes essential to the invention. UV absorbingcompounds may be included in some or all of the packaging.

When in the form of a liquid, the laundry care compositions of theinvention may be aqueous (typically above 2 wt % or even above 5 or 10wt % total water, up to 90 or up to 80 wt % or 70 wt % total water) ornon-aqueous (typically below 2 wt % total water content). Typically thecompositions of the invention will be in the form of an aqueous solutionor uniform dispersion or suspension of surfactant, shading dye, andcertain optional other ingredients, some of which may normally be insolid form, that have been combined with the normally liquid componentsof the composition, such as the liquid alcohol ethoxylate nonionic, theaqueous liquid carrier, and any other normally liquid optionalingredients. Such a solution, dispersion or suspension will beacceptably phase stable. When in the form of a liquid, the laundry carecompositions of the invention preferably have viscosity from 1 to 1500centipoises (1-1500 mPa*s), more preferably from 100 to 1000 centipoises(100-1000 mPa*s), and most preferably from 200 to 500 centipoises(200-500 mPa*s) at 20s-1 and 21° C. Viscosity can be determined byconventional methods. Viscosity may be measured using an AR 550rheometer from TA instruments using a plate steel spindle at 40 mmdiameter and a gap size of 500 am. The high shear viscosity at 20s-1 andlow shear viscosity at 0.05-1 can be obtained from a logarithmic shearrate sweep from 0.1-1 to 25-1 in 3 minutes time at 21° C. The preferredrheology described therein may be achieved using internal existingstructuring with detergent ingredients or by employing an externalrheology modifier. More preferably the laundry care compositions, suchas detergent liquid compositions have a high shear rate viscosity offrom about 100 centipoise to 1500 centipoise, more preferably from 100to 1000 cps. Unit Dose laundry care compositions, such as detergentliquid compositions have high shear rate viscosity of from 400 to 1000cps. Laundry care compositions such as laundry softening compositionstypically have high shear rate viscosity of from 10 to 1000, morepreferably from 10 to 800 cps, most preferably from 10 to 500 cps. Handdishwashing compositions have high shear rate viscosity of from 300 to4000 cps, more preferably 300 to 1000 cps.

The liquid compositions, preferably the laundry care composition hereincan be prepared by combining the components thereof in any convenientorder and by mixing, e.g., agitating, the resulting componentcombination to form a phase stable liquid laundry care composition. In aprocess for preparing such compositions, a liquid matrix is formedcontaining at least a major proportion, or even substantially all, ofthe liquid components, e.g., nonionic surfactant, the non-surface activeliquid carriers and other optional liquid components, with the liquidcomponents being thoroughly admixed by imparting shear agitation to thisliquid combination. For example, rapid stirring with a mechanicalstirrer may usefully be employed. While shear agitation is maintained,substantially all of any anionic surfactants and the solid formingredients can be added. Agitation of the mixture is continued, and ifnecessary, can be increased at this point to form a solution or auniform dispersion of insoluble solid phase particulates within theliquid phase. After some or all of the solid-form materials have beenadded to this agitated mixture, particles of any enzyme material to beincluded, e.g., enzyme prills, are incorporated. As a variation of thecomposition preparation procedure hereinbefore described, one or more ofthe solid components may be added to the agitated mixture as a solutionor slurry of particles premixed with a minor portion of one or more ofthe liquid components. After addition of all of the compositioncomponents, agitation of the mixture is continued for a period of timesufficient to form compositions having the requisite viscosity and phasestability characteristics. Frequently this will involve agitation for aperiod of from about 30 to 60 minutes.

The leuco colorants of the present invention have been found to besuitable for use in liquid laundry care compositions having a wide rangeof pH values. For example, the inventive leuco colorants have been foundto be suitable for use in liquid laundry care compositions having a pHof greater than or equal to 10. The inventive leuco colorants have alsobeen found to be suitable for use in liquid laundry care compositionshaving a pH of less than 10. Thus, the leuco colorant are stable inlaundry care compositions having pH values of greater than or equal to10 and less than or equal to 10.

Pouches. In a preferred embodiment of the invention, the composition isprovided in the form of a unitized dose, either tablet form orpreferably in the form of a liquid/solid (optionally granules)/gel/pasteheld within a water-soluble film in what is known as a pouch or pod. Thecomposition can be encapsulated in a single or multi-compartment pouch.Multi-compartment pouches are described in more detail in EP-A-2133410.When the composition is present in a multi-compartment pouch, thecomposition of the invention may be in one or two or more compartments,thus the dye may be present in one or more compartments, optionally allcompartments. Non-shading dyes or pigments or other aesthetics may alsobe used in one or more compartments. In one embodiment the compositionis present in a single compartment of a multi-compartment pouch.

Preferred film materials are polymeric materials. The film material canbe obtained, for example, by casting, blow-molding, extrusion or blownextrusion of the polymeric material, as known in the art. Preferredpolymers, copolymers or derivatives thereof suitable for use as pouchmaterial are selected from polyvinyl alcohols, polyvinyl pyrrolidone,polyalkylene oxides, acrylamide, acrylic acid, cellulose, celluloseethers, cellulose esters, cellulose amides, polyvinyl acetates,polycarboxylic acids and salts, polyaminoacids or peptides, polyamides,polyacrylamide, copolymers of maleic/acrylic acids, polysaccharidesincluding starch and gelatine, natural gums such as xanthum andcarragum. More preferred polymers are selected from polyacrylates andwater-soluble acrylate copolymers, methylcellulose,carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin,polymethacrylates, and most preferably selected from polyvinyl alcohols,polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC),and combinations thereof. Preferably, the level of polymer in the pouchmaterial, for example a PVA polymer, is at least 60%. The polymer canhave any weight average molecular weight, preferably from about 1000 to1,000,000, more preferably from about 10,000 to 300,000 yet morepreferably from about 20,000 to 150,000. Mixtures of polymers can alsobe used as the pouch material. This can be beneficial to control themechanical and/or dissolution properties of the compartments or pouch,depending on the application thereof and the required needs. Suitablemixtures include for example mixtures wherein one polymer has a higherwater-solubility than another polymer, and/or one polymer has a highermechanical strength than another polymer. Also suitable are mixtures ofpolymers having different weight average molecular weights, for examplea mixture of PVA or a copolymer thereof of a weight average molecularweight of about 10,000-40,000, preferably around 20,000, and of PVA orcopolymer thereof, with a weight average molecular weight of about100,000 to 300,000, preferably around 150,000. Also suitable herein arepolymer blend compositions, for example comprising hydrolyticallydegradable and water-soluble polymer blends such as polylactide andpolyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol,typically comprising about 1-35% by weight polylactide and about 65% to99% by weight polyvinyl alcohol. Preferred for use herein are polymerswhich are from about 60% to about 98% hydrolysed, preferably about 80%to about 90% hydrolysed, to improve the dissolution characteristics ofthe material.

Naturally, different film material and/or films of different thicknessmay be employed in making the compartments of the present invention. Abenefit in selecting different films is that the resulting compartmentsmay exhibit different solubility or release characteristics.

Most preferred film materials are PVA films known under the MonoSoltrade reference M8630, M8900, H8779 and those described in U.S. Pat.Nos. 6,166,117 and 6,787,512 and PVA films of corresponding solubilityand deformability characteristics.

The film material herein can also comprise one or more additiveingredients. For example, it can be beneficial to add plasticizers, forexample glycerol, ethylene glycol, diethyleneglycol, propylene glycol,sorbitol and mixtures thereof. Other additives include functionaldetergent additives to be delivered to the wash water, for exampleorganic polymeric dispersants, etc.

Solid Form. As noted previously, the laundry care compositions may be ina solid form. Suitable solid forms include tablets and particulateforms, for example, granular particles, flakes or sheets. Varioustechniques for forming detergent compositions in such solid forms arewell known in the art and may be used herein. In one aspect, for examplewhen the composition is in the form of a granular particle, the leucocolorant is provided in particulate form, optionally includingadditional but not all components of the laundry detergent composition.The colorant particulate is combined with one or more additionalparticulates containing a balance of components of the laundry detergentcomposition. Further, the colorant, optionally including additional butnot all components of the laundry care composition, may be provided inan encapsulated form, and the shading dye encapsulate is combined withparticulates containing a substantial balance of components of thelaundry care composition.

Method of Use. The compositions of this invention, prepared ashereinbefore described, can be used to form aqueous washing/treatmentsolutions for use in the laundering/treatment of fabrics.

Generally, an effective amount of such compositions is added to water,for example in a conventional fabric automatic washing machine, to formsuch aqueous laundering solutions. The aqueous washing solution soformed is then contacted, typically under agitation, with the fabrics tobe laundered/treated therewith. An effective amount of the liquiddetergent compositions herein added to water to form aqueous launderingsolutions can comprise amounts sufficient to form from about 500 to7,000 ppm of composition in aqueous washing solution, or from about1,000 to 3,000 ppm of the laundry care compositions herein will beprovided in aqueous washing solution.

Typically, the wash liquor is formed by contacting the laundry carecomposition with wash water in such an amount so that the concentrationof the laundry care composition in the wash liquor is from above 0 g/lto 5 g/l, or from 1 g/l, and to 4.5 g/l, or to 4.0 g/l, or to 3.5 g/l,or to 3.0 g/l, or to 2.5 g/l, or even to 2.0 g/l, or even to 1.5 g/l.The method of laundering fabric or textile may be carried out in atop-loading or front-loading automatic washing machine, or can be usedin a hand-wash laundry application. In these applications, the washliquor formed and concentration of laundry detergent composition in thewash liquor is that of the main wash cycle. Any input of water duringany optional rinsing step(s) is not included when determining the volumeof the wash liquor.

The wash liquor may comprise 40 liters or less of water, or 30 liters orless, or 20 liters or less, or 10 liters or less, or 8 liters or less,or even 6 liters or less of water. The wash liquor may comprise fromabove 0 to 15 liters, or from 2 liters, and to 12 liters, or even to 8liters of water. Typically from 0.01 kg to 2 kg of fabric per liter ofwash liquor is dosed into said wash liquor. Typically from 0.01 kg, orfrom 0.05 kg, or from 0.07 kg, or from 0.10 kg, or from 0.15 kg, or from0.20 kg, or from 0.25 kg fabric per liter of wash liquor is dosed intosaid wash liquor. Optionally, 50 g or less, or 45 g or less, or 40 g orless, or 35 g or less, or 30 g or less, or 25 g or less, or 20 g orless, or even 15 g or less, or even 10 g or less of the composition iscontacted to water to form the wash liquor. Such compositions aretypically employed at concentrations of from about 500 ppm to about15,000 ppm in solution. When the wash solvent is water, the watertemperature typically ranges from about 5° C. to about 90° C. and, whenthe situs comprises a fabric, the water to fabric ratio is typicallyfrom about 1:1 to about 30:1. Typically the wash liquor comprising thelaundry care composition of the invention has a pH of from 3 to 11.5.

In one aspect, such method comprises the steps of optionally washingand/or rinsing said surface or fabric, contacting said surface or fabricwith any composition disclosed in this specification then optionallywashing and/or rinsing said surface or fabric is disclosed, with anoptional drying step.

Drying of such surfaces or fabrics may be accomplished by any one of thecommon means employed either in domestic or industrial settings. Thefabric may comprise any fabric capable of being laundered in normalconsumer or institutional use conditions, and the invention is suitablefor cellulosic substrates and in some aspects also suitable forsynthetic textiles such as polyester and nylon and for treatment ofmixed fabrics and/or fibers comprising synthetic and cellulosic fabricsand/or fibers. As examples of synthetic fabrics are polyester, nylon,these may be present in mixtures with cellulosic fibers, for example,polycotton fabrics. The solution typically has a pH of from 7 to 11,more usually 8 to 10.5. The compositions are typically employed atconcentrations from 500 ppm to 5,000 ppm in solution. The watertemperatures typically range from about 5° C. to about 90° C. The waterto fabric ratio is typically from about 1:1 to about 30:1.

Thus, in another embodiment, the invention provides a method of treatinga textile. The method preferably comprises the steps of (i) treating atextile with an aqueous solution containing a composition as describedherein, (ii) optionally, rinsing the textile, and (iii) drying thetextile. In one aspect, the invention provides a method of treating atextile comprising the steps of: (i) treating a textile with an aqueoussolution containing a compound as described herein, the aqueous solutioncomprising from 10 ppb to 5000 ppm of at least one such compound andfrom 0.0 g/L to 3 g/L of a surfactant; (ii) optionally rinsing; and(iii) drying the textile. The compound utilized in this method can beany of the compounds described herein. Further, the aqueous solutionutilized in the method can be created by adding a compound directly toan aqueous medium or by adding a laundry care composition containing aleuco composition to an aqueous medium.

Test Methods

Fabric swatches used in the test methods herein are obtained fromTestfabrics, Inc. West Pittston, Pa., and are 100% Cotton, Style 403(cut to 2″×2″) and/or Style 464 (cut to 4″×6″), and an unbrightenedmultifiber fabric, specifically Style 41 (5 cm×10 cm).

All reflectance spectra and color measurements, including L*, a*, b*,K/S, and Whiteness Index (WI CIE) values on dry fabric swatches, aremade using one of four spectrophotometers: (1) a Konica-Minolta 3610dreflectance spectrophotometer (Konica Minolta Sensing Americas, Inc.,Ramsey, N.J., USA; D65 illumination, 10° observer, UV light excluded),(2) a LabScan XE reflectance spectrophotometer (HunterLabs, Reston, Va.;D65 illumination, 10° observer, UV light excluded), (3) a Color-Eye®7000A (GretagMacbeth, New Windsor, N.Y., USA; D65 light, UV excluded),or (4) a Color i7 spectrophotometer (X-rite, Inc., Grand Rapids, Mich.,USA; D65 light, UV excluded).

Where fabrics are irradiated, unless otherwise indicated, the specifiedfabrics post-dry are exposed to simulated sunlight with irradiance of0.77 W/m² @ 420 nm in an Atlas Xenon Fade-Ometer Ci3000+(Atlas MaterialTesting Technology, Mount Prospect, Ill., USA) equipped with Type SBorosilicate inner (Part no. 20277300) and outer (Part no. 20279600)filters, set at 37° C. maximum cabinet temperature, 57° C. maximum blackpanel temperature (BPT black panel geometry), and 35% RH (relativehumidity). Unless otherwise indicated, irradiation is continuous overthe stated duration.

I. Method for Determining Leuco Conjugate Efficiency from a WashSolution

Cotton swatches (Style 464) are stripped prior to use by washing at 49°C. two times with heavy duty liquid laundry detergent nil brightener(1.55 g/L in aqueous solution). A concentrated stock solution of eachleuco conjugate to be tested is prepared in a solvent selected fromethanol or 50:50 ethanol:water, preferably ethanol.

All L*, a*, b* and Whiteness Index (WI CIE) values for the cottonfabrics are measured on the dry swatches using a Konica-Minolta 3610dreflectance spectrophotometer.

A base wash solution is prepared by dissolving AATCC heavy duty liquidlaundry detergent nil brightener (5.23 g/1.0 L) in deionized water. Fourstripped cotton swatches are weighed together and placed in a 250 mLErlenmeyer flask along with two 10 mm glass marbles. A total of threesuch flasks are prepared for each wash solution to be tested. The basewash solution is dosed with the leuco conjugate stock to achieve a washsolution with the desired 2.00×10⁻⁶ equivalents/L wash concentration ofthe leuco conjugate.

An aliquot of this wash solution sufficient to provide a 10.0:1.0liquor:fabric (w/w) ratio is placed into each of the three 250 mLErlenmeyer flasks. Each flask is dosed with a 1000 gpg stock hardnesssolution to achieve a final wash hardness of 6 gpg (3:1 Ca:Mg).

The flasks are placed on a Model 75 wrist action shaker (BurrellScientific, Inc., Pittsburgh, Pa.) and agitated at the maximum settingfor 12 minutes, after which the wash solution is removed by aspiration,a volume of rinse water (0 gpg) equivalent to the amount of washsolution used is added. Each flask is dosed with a 1000 gpg stockhardness solution to achieve a final rinse hardness of 6 gpg (3:1 Ca:Mg)before agitating 4 more minutes. The rinse is removed by aspiration andthe fabric swatches are spun dry (Mini Countertop Spin Dryer, TheLaundry Alternative Inc., Nashua, N.H.) for 1 minute, then placed in afood dehydrator set at 135° F. to dry in the dark for 2 hours. Followingthis drying procedure, the samples can be stored in the dark or exposedto light for varying amounts of time before measuring the properties ofthe fabric.

Because consumer habits vary greatly throughout the world, the methodsused must allow for the possibility of measuring the benefits of leucocompounds across conditions. One such condition is the exposure to lightfollowing drying. Some leuco compounds will not exhibit as large abenefit under dark storage as under light storage, so each leucocompound must be tested under both sets of conditions to determine theoptimum benefit. Therefore Method I includes exposure of the driedfabrics to simulated sunlight for various increments of time beforemeasurements are taken, and the LCE value is set to the maximum valueobtained from the set of exposure times described below.

A. Dark Conditions Post-Dry

After drying, the fabrics are stored in the dark at room temperaturebetween measurement time points. L*, a*, b* and Whiteness Index (WI CIE)values for the cotton fabrics are measured at time t=0, 6, 24 and 48hours after the conclusion of the two hour drying period. The values ofthe 12 swatches generated for each leuco colorant (three flasks withfour swatches each) are averaged to arrive at the sample values for L*,a*, b* and WI CIE at each time point t.

In order to obtain L*, a*, b* and Whiteness Index (WI CIE) values forthe control treatment, the above procedure is repeated as described withthe following exceptions: (1) the control base wash solution is preparedusing AATCC heavy duty liquid laundry detergent nil brightener (5.23g/1.0 L) in deionized water, and (2) the values of the 12 swatchesgenerated for the control measured after the drying period are averagedto arrive at the sample values for L*, a*, b* and WI CIE and the controlvalue at t=0 is also used as the control values for t=6, 24 and 48hours.

The leuco colorant efficiency (LCE) of the leuco colorant in the laundrycare formulation is calculated based on the data collected at each timepoint t using the following equation:

LCE_(t)=DE*=((L*_(c)−L*_(s))²+(a* _(c) −a* _(s))²+(b* _(c) −b*_(s))²)^(1/2)

wherein the subscripts c and s respectively refer to the control, i.e.,the fabric washed in AATCC heavy duty liquid laundry detergent nilbrightener, and the sample, i.e., the fabric washed in the laundry careformualtion containing leuco colorant, where the values used tocalculate LCE_(t) are those at the corresponding time points t (0, 6, 24or 48 hours).

The WI CIE values of the 12 swatches generated for each wash solution(three flasks with four swatches each) are averaged and the change inwhiteness index on washing is calculated using the following equation:

ΔWI=WI CIE (after wash)−WI CIE (before wash)

There will be a separate value for the laundry care formulation(ΔWI_(sample)) and the AATCC HDL nil brightener (ΔWI_(control)). Thechange in whiteness between the two formulations is given by:

δΔWI=ΔWI_(sample)−ΔWI_(control)

B. Light Conditions Post-Dry

The specified cotton fabrics post-dry are exposed to simulated sunlightfor 15 min, 30 min, 45 min, 60 min, 75 min, 90 min, 120 min, and 240min. The L*, a*, b* and Whiteness Index (WI CIE) values for the cottonfabrics are measured on the swatches after each exposure period. Thecalculation of the LCE and the ΔWI value at each exposure time point isas described in Method I.A. above, and the LCE values and the ΔWI valuesfor the sample and control laundry care formulations are set to themaximum values obtained from the set of exposure times listed.

II. Method for Determining Relative Hue Angle (Vs. AATCC Control) Therelative hue angle delivered by a leuco colorant to cotton fabricstreated according to Method I described above is determined as follows.

-   -   a) The a* and b* values of the 12 swatches from each solution        are averaged and the following formulas used to determine Δa*        and Δb*:

Δa*=a* _(s) −a* _(c) and Δb*=b* _(s) −b* _(c)

-   -   -   wherein the subscripts c and s respectively refer to the            fabric washed in AATCC Heavy duty liquid detergent nil            brightener (control) and the fabric washed in the laundry            care formulation containing leuco colorant (sample).

    -   b) If the absolute value of both Δa* and Δb*<0.25, no Relative        Hue Angle (RHA) is calculated. If the absolute value of either        Δa* or Δb* is ≥0.25, the RHA is determined using one of the        following formulas:

RHA=ATAN2(Δa*,Δb*) for Δb*≥0

RHA=360+ATAN2(Δa*,Δb*) for Δb*<0

A relative hue angle can be calculated for each time point where data iscollected in either the dark post-dry or light post-dry assessments. Anyof these points may be used to satisfy the requirements of a claim.

III. Method for Determining Leuco Conjugate Efficiency from a WashSolution

Cotton swatches (Testfabrics, Inc. West Pittston, Pa.; Style 464, 100%Cotton, cut to 4″ x 6″) are stripped prior to use by washing at 49° C.two times with heavy duty liquid laundry detergent nil brightener (1.55g/L in aqueous solution). A concentrated stock solution of each leucoconjugate to be tested is prepared in a solvent selected from ethanol or50:50 ethanol:water, preferably ethanol.

All L*, a*, b* and Whiteness Index (WI CIE) values for the cottonfabrics are measured on the dry swatches using a Konica-Minolta 3610dreflectance spectrophotometer (Konica Minolta Sensing Americas, Inc.,Ramsey, N.J., USA; D65 illumination, 10° observer, UV light excluded).

A base wash solution is prepared by dissolving AATCC heavy duty liquidlaundry detergent nil brightener (5.23 g/1.0 L) in deionized water. Fourstripped cotton swatches are weighed together and placed in a 250 mLErlenmeyer flask along with two 10 mm glass marbles. A total of threesuch flasks are prepared for each wash solution to be tested. The basewash solution is dosed with the leuco conjugate stock to achieve a washsolution with the desired 2.00×10⁻⁶ equivalents/L wash concentration ofthe leuco conjugate.

An aliquot of this wash solution sufficient to provide a 10.0:1.0liquor:fabric (w/w) ratio is placed into each of the three 250 mLErlenmeyer flasks. Each flask is dosed with a 1000 gpg stock hardnesssolution to achieve a final wash hardness of 6 gpg (3:1 Ca:Mg).

The flasks are placed on a Model 75 wrist action shaker (BurrellScientific, Inc., Pittsburgh, Pa.) and agitated at the maximum settingfor 12 minutes, after which the wash solution is removed by aspiration,a volume of rinse water (0 gpg) equivalent to the amount of washsolution used is added. Each flask is dosed with a 1000 gpg stockhardness solution to achieve a final rinse hardness of 6 gpg (3:1 Ca:Mg)before agitating 4 more minutes. The rinse is removed by aspiration andthe fabric swatches are spun dry (Mini Countertop Spin Dryer, TheLaundry Alternative Inc., Nashua, N.H.) for 1 minute, then placed in afood dehydrator set at 135° F. to dry in the dark for 2 hours. Followingthis drying procedure, the samples can be stored in the dark or exposedto light for varying amounts of time before measuring the properties ofthe fabric.

IV. Method for Determination of Surface Tension Value for a LeucoColorant and Oxidized Form Thereof.

The material to be tested is either a leuco colorant according to theinstant invention, or the dye that represents the second colored stateof the leuco colorant (for example, a triarylmethane dye). A total of250-255 mg of the material to be tested is weighed into a 4 oz. glassjar and 50.0 mL deionized water (Barnstead B-Pure System, about 17.27ohm) is added along with a magnetic stir bar. The jar is capped, placedon a magnetic stir plate, and the mixture stirred for one hour at 22.0°C. Thereafter the stirring is stopped and the mixture left to standundisturbed for one hour. At the end of that time, 10.0 mL of solutionis pulled into a syringe which is then fitted with a glass fiberAcrodisc® filter and the aliquot filtered into a 20 mL scintillationvial. A VWR LabMax Pipettor is used to pipette to deliver 45.0microliters of the filtered solution into each of eight separate wellsof a 96-well plate. The solutions are tested at approximately 22.0° C.with a Kibron Delta 8 Tensiometer and the average value of the eightmeasured replicates reported as the Surface Tension Value in mN/m.

Example 1

This example demonstrates the preparation of a compound according to theinvention and having the following structure

12.45 grams of 4-acetamidobenzaldehyde and aniline-2,4 (anilinealkoxylated with 2 EO and 4 PO on average) were added to a three neckround bottom flask equipped with a heating mantle, stirrer, condenserand nitrogen inlet. Then, 2.71 grams of urea was dissolved in 18 gramsof water, and the solution was added to the reaction. After mixing,23.74 grams of concentrated HCl (37%) was added slowly to the reactionmixture while keeping the temperature below 90° C. The reaction mixturewas stirred at 90° C. under nitrogen for 6 hours. After reactioncompletion, the contents of the flask were added into an excess amountof a sodium bicarbonate solution (30 g in 600 mL water). The product wasextracted from the resulting mixture using ethyl acetate and washed withDI water. The ethyl acetate was removed using a rotovap, and theresultant product was dried via vacuum oven.

Example 2

This example demonstrates the preparation of a compound according to theinvention and having the following structure

15 grams of 4-nitrobenzaldehyde and 36.98 grams ofN-phenyldiethanolamine was charged into a 250 mL round-bottom flaskequipped with an overhead mechanical stirrer, thermocouple, condenser,and nitrogen inlet. A solution of urea in water (3.52 grams of urea in20 mL of water) was added to the reaction mixture. While stirring, 30.16grams of HCl (37 wt. %) was slowly charged into the reaction mixturewhile carefully monitoring the temperature for exotherms. Then, thereaction mixture was heated to 95° C. and stirred overnight undernitrogen. On the second day, the reaction mixture was neutralized withan excess amount of a sodium bicarbonate solution (5 wt. % in water).The product was retrieved by extraction with ethyl acetate, followed bywashing with DI water, drying with magnesium sulfate, filtering andfinally removing the solvent using a rotovap.

After drying, 11.25 g of the product made above was dissolved into 30grams of ethanol in a 250 mL round bottom flask equipped with amechanical stirrer and temperature probe. To this mixture, about 15grams of iron powder was added. Then, a solution of HCl (3 grams of 37%HCl mixed with 40 gram water) was added slowly to the solution and thereaction mixture was heated to reflux for 2 hours. After cooling toambient temperature, the reaction mixture was filtered to remove theiron powder. Then, the filtrate was neutralized with an excess amount of5% sodium bicarbonate solution. The product was then collected byfiltration and re-dissolved in ethanol. After filtering once more toremove insoluble impurities, the product was isolated by evaporating thesolvent using a rotovap.

Example 3

This example demonstrates the preparation of a compound according to theinvention and having the following structure

7.5 grams of the product obtained in Example 2 was dissolved in about110 grams of methyl ethyl ketone. 7.43 grams of chloranil was added, andthe reaction mixture was heated to reflux for 1 hour. After the reactioncooled to ambient temperature, 44.35 grams of 5 mol/L HCl solution wasadded, and the reaction mixture was stirred. After evaporating off themethyl ethyl ketone, the aqueous solution was filtered to removeinsoluble impurities. The filtrate was washed with diethyl ether tofurther remove residual impurities, and then dried via rot-vap toisolate the product. The molar extinction coefficient of the isolatecompound was measured in methanol to be about 55,000 L/mol/cm at 578 nm.

Example 4

This example compares the hueing effects of the compound of Example 2and LCV 4EO (comparative example, see below for molecular structure)

The hue effects of these compounds were tested and compared via amulti-wash experiment using a mini-washer according to the followingprocedure. Three different detergent samples were tested. The first is acommercially available HDL detergent. The second is the samecommercially available HDL detergent with LCV4EO added at a loading of1,000 ppm. The third is the same commercially available HDL detergentwith the compound of Example 2 added at a loading of 1,000 ppm.

In each wash test, twelve pieces of bleached cotton t-shirt fabric(purchased from Testfabrics, Inc., style number 437W-60, cut to 6″ by 6″size) were added to a wash water solution containing the detergent andwashed with the mini washer (Haier Portable washer XQBM22-C).Approximately 12 L of DI water was used during wash cycle, and the washwater: Fabric: HDL ratio was 1000:40:1 (by mass) using about 480 gram ofcotton dummy load. After the first wash, the fabric was rinsed in thesame mini washer twice using 12 L of DI water each time. Four of thefabrics were then removed from the washer and dried in a drier, and theCIE L*, a*, and b* values were read with a color eye spectrophotometer.The remaining eight sample fabrics were then washed two more times andrinsed as described above, and four more sample fabrics were removedfrom the washer, dried, and analyzed using the spectrophotometer. Theremaining four samples of the cotton fabric were then washed two moretimes, rinsed as described above, dried, and analyzed using thespectrophotometer.

The bluing effect of the LCV4EO and the compound of Example 2 wascharacterized by the change in b* values (delta b*) of the fabricswashed with the detergents when compared with the fabric before wash.The more negative delta b* means better bluing. The delta b* values fromthe three detergent samples were listed in the table below. The HDLdetergent showed some negative delta b* values as it contains someoptical brightener. However, it was clear that the detergent containinga leuco compound is more efficient in bluing.

The bluing effect of the LCV4EO and the compound of Example 2 was alsocharacterized by measuring the relative hue angle imparted to thefabrics. In this particular example, the relative hue angle wasdetermined as follows:

-   -   1) The a* and b* values of the swatches and the following        formulas used to determine Δa* and Δb*:

Δa*=a* _(L) −a*s and Δb*=b*L−b*s

-   -   -   wherein the subscripts L and S respectively refer to the            fabric washed in the heavy duty liquid detergent containing            leuco colorants (LCV 4EO and the product of Example 2) and            the starting fabric before wash.

    -   2) If the absolute value of both Δa* and Δb*<0.25, no Relative        Hue Angle (RHA) is calculated. If the absolute value of either        Δa* or Δb* is >0.25, the RHA is determined using one of the        following formulas:

RHA=ATAN2(Δa*,Δb*) for Δb*≥0

RHA=360+ATAN2(Δa*,Δb*) for Δb*<0

TABLE 1 delta b* of the fabrics after 1, 3, and 5 washes. Detergent HDLplus 1000 ppm HDL plus 1000 ppm Wash # HDL of LCV 4EO of Example II 0 00 0 1 −0.47 −0.91 −1.03 3 −0.71 −1.18 −1.31 5 −0.71 −1.31 −1.39

TABLE 2 Relative hue angle of the fabric after 1, 3, and 5 washes.Detergent HDL plus 1000 ppm HDL plus 1000 ppm Wash # of LCV 4EO ofExample II 0 — — 1 260 280 3 257 277 5 260 273

Compared with LCV 4EO, the compound of Example 2 shows about the samebluing effect as demonstrated in the delta b* value in Table 1 above.However, the compound of Example 2 has a more desirable hue. Table 2compares the relative hue angle (RHA) of the fabrics washed with LCV4EOand the compound of Example 2. Clearly, the LCV4EO delivers a greenishblue hue (RHA in the range of 225 to 270), while the compound of Example2 delivers a RHA of about 277 degrees. For bluing purposes, the mostdesirable hue has a relative hue angle from 270 to 300.

FORMULATION EXAMPLES

The following are illustrative examples of cleaning compositionsaccording to the present disclosure and are not intended to be limiting.

Examples 1-7: Heavy Duty Liquid Laundry Detergent Compositions

1 2 3 4 5 6 7 Ingredients % weight AE_(1.8)S 6.77 5.16 1.36 1.30 — — —AE₃S — — — — 0.45 — — LAS 0.86 2.06 2.72 0.68 0.95 1.56 3.55 HSAS 1.852.63 1.02 — — — — AE9 6.32 9.85 10.20  7.92 AE8 35.45  AE7 8.40 12.44 C₁₂₋₁₄ dimethyl Amine Oxide 0.30 0.73 0.23 0.37 — — — C₁₂₋₁₈ Fatty Acid0.80 1.90 0.60 0.99 1.20 — 15.00  Citric Acid 2.50 3.96 1.88 1.98 0.902.50 0.60 Optical Brightener 1 1.00 0.80 0.10 0.30 0.05 0.50  0.001Optical Brightener 3  0.001 0.05 0.01 0.20 0.50 — 1.00 Sodium formate1.60 0.09 1.20 0.04 1.60 1.20 0.20 DTI 0.32 0.05 — 0.60 — 0.60 0.01Sodium hydroxide 2.30 3.80 1.70 1.90 1.70 2.50 2.30 Monoethanolamine1.40 1.49 1.00 0.70 — — — Diethylene glycol 5.50 — 4.10 — — — — Chelant1 0.15 0.15 0.11 0.07 0.50 0.11 0.80 4-formyl-phenylboronic acid — — — —0.05 0.02 0.01 Sodium tetraborate 1.43 1.50 1.10 0.75 — 1.07 — Ethanol1.54 1.77 1.15 0.89 — 3.00 7.00 Polymer 1 0.10 — — — — — 2.00 Polymer 20.30 0.33 0.23 0.17 — — — Polymer 3 — — — — — — 0.80 Polymer 4 0.80 0.810.60 0.40 1.00 1.00 — 1,2-Propanediol — 6.60 — 3.30 0.50 2.00 8.00Structurant 0.10 — — — — — 0.10 Perfume 1.60 1.10 1.00 0.80 0.90 1.501.60 Perfume encapsulate 0.10 0.05 0.01 0.02 0.10 0.05 0.10 Protease0.80 0.60 0.70 0.90 0.70 0.60 1.50 Mannanase 0.07 0.05  0.045 0.06 0.04 0.045 0.10 Amylase 1 0.30 — 0.30 0.10 — 0.40 0.10 Amylase 2 — 0.20 0.100.15 0.07 — 0.10 Xyloglucanase 0.20 0.10 — — 0.05 0.05 0.20 Lipase 0.400.20 0.30 0.10 0.20 — — Polishing enzyme — 0.04 — — —  0.004 — Nuclease0.05 — — — — —  0.003 Dispersin B — — — 0.05 0.03  0.001  0.001Liquitint ® V200 0.01 — — — — —  0.005 Leuco Conjugate 0.5  0.35 0.1 0.2  0.04 0.02 0.04 Dye control agent — 0.3  — 0.03 — 0.3  0.3  Water,dyes & minors Balance pH 8.2 Based on total cleaning and/or treatmentcomposition weight. Enzyme levels are reported as raw material.

Examples 8 to 18: Unit Dose Compositions

These examples provide various formulations for unit dose laundrydetergents. Compositions 8 to 12 comprise a single unit dosecompartment. The film used to encapsulate the compositions ispolyvinyl-alcohol-based film.

8 9 10 11 12 Ingredients % weight LAS 19.09 16.76 8.59 6.56 3.44 AE3S1.91 0.74 0.18 0.46 0.07 AE7 14.00 17.50 26.33 28.08 31.59 Citric Acid0.6 0.6 0.6 0.6 0.6 C12-15 Fatty Acid 14.8 14.8 14.8 14.8 14.8 Polymer 34.0 4.0 4.0 4.0 4.0 Chelant 2 1.2 1.2 1.2 1.2 1.2 Optical Brightener 10.20 0.25 0.01 0.01 0.50 Optical Brightener 2 0.20 — 0.25 0.03 0.01Optical Brightener 3 0.18 0.09 0.30 0.01 — DTI 0.10 — 0.20 — — Glycerol6.1 6.1 6.1 6.1 6.1 Monoethanol amine 8.0 8.0 8.0 8.0 8.0Tri-isopropanol amine — — 2.0 — — Tri-ethanol amine — 2.0 — — — Cumenesulfonate — — — — 2.0 Protease 0.80 0.60 0.07 1.00 1.50 Mannanase 0.070.05 0.05 0.10 0.01 Amylase 1 0.20 0.11 0.30 0.50 0.05 Amylase 2 0.110.20 0.10 — 0.50 Polishing enzyme 0.005 0.05 — — — Nuclease 0.— 0.05 — —0.005 Dispersin B 0.010 0.05 0.005 0.005 — Cyclohexyl dimethanol — — —2.0 — Leuco conjugate 0.6 0.3 1.0 0.1 0.4 Liquitint ® V200 — — 0.01 0.05— Structurant 0.14 0.14 0.14 0.14 0.14 Perfume 1.9 1.9 1.9 1.9 1.9 Dyecontrol agent 0.1 0.3 0.2 0.5 0.3 Water and miscellaneous To 100% pH7.5-8.2 Based on total cleaning and/or treatment composition weight.Enzyme levels are reported as raw material.

In the following examples the unit dose has three compartments, butsimilar compositions can be made with two, four or five compartments.The film used to encapsulate the compartments is polyvinyl alcohol.

Base compositions 13 14 15 16 Ingredients % weight HLAS 26.82 16.35 7.503.34 AE7 17.88 16.35 22.50 30.06 Citric Acid 0.5 0.7 0.6 0.5 C12-15Fatty acid 16.4 6.0 11.0 13.0 Polymer 1 2.9 0.1 — — Polymer 3 1.1 5.12.5 4.2 Cationic cellulose polymer — — 0.3 0.5 Polymer 6 — 1.5 0.3 0.2Chelant 2 1.1 2.0 0.6 1.5 Optical Brightener 1 0.20 0.25 0.01 0.005Optical Brightener 3 0.18 0.09 0.30 0.005 DTI 0.1 — 0.05 — Glycerol 5.35.0 5.0 4.2 Monoethanolamine 10.0 8.1 8.4 7.6 Polyethylene glycol — —2.5 3.0 Potassium sulfite 0.2 0.3 0.5 0.7 Protease 0.80 0.60 0.40 0.80Amylase 1 0.20 0.20 0.200 0.30 Polishing enzyme — — 0.005 0.005 Nuclease0.05 — — — Dispersin B — 0.010 0.010 0.010 MgCl₂ 0.2 0.2 0.1 0.3Structurant 0.2 0.1 0.2 0.2 Acid Violet 50 0.04 0.03 0.05 0.03Perfume/encapsulates 0.10 0.30 0.01 0.05 Dye control agent 0.2 0.03 0.4— Solvents and misc. To 100% pH 7.0-8.2 Finishing compositions 17 18Compartment A B C A B C Volume of each compartment 40 ml 5 ml 5 ml 40 ml5 ml 5 ml Ingredients Active material in Wt. % Perfume 1.6 1.6 1.6 1.61.6 1.6 Liquitint ® V200 0 0.006 0 0 0.004 — Leuco conjugate 0.2 0.4 — —TiO2 — — 0.1 — 0.1 Sodium Sulfite 0.4 0.4 0.4 0.1 0.3 0.3 Polymer 5 — 2— — Hydrogenated castor oil 0.14 0.14 0.14 0.14 0.14 0.14 BaseComposition 13, 14, 15 Add to 100% or 16

Based on total cleaning and/or treatment composition weight, enzymelevels are reported as raw material.

-   -   AE1.8S is C₁₂₋₁₅ alkyl ethoxy (1.8) sulfate    -   AE3S is C₁₂₋₁₅ alkyl ethoxy (3) sulfate    -   AE7 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of        ethoxylation of 7    -   AE8 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of        ethoxylation of 8    -   AE9 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of        ethoxylation of 9    -   Amylase 1 is Stainzyme®, 15 mg active/g, supplied by Novozymes    -   Amylase 2 is Natalase®, 29 mg active/g, supplied by Novozymes    -   Xyloglucanase is Whitezyme®, 20 mg active/g, supplied by        Novozymes    -   Chelant 1 is diethylene triamine pentaacetic acid    -   Chelant 2 is 1-hydroxyethane 1,1-diphosphonic acid    -   Dispersin B is a glycoside hydrolase, reported as 1000 mg        active/g    -   DTI is either poly(4-vinylpyridine-1-oxide) (such as Chromabond        S-403E®), or poly(1-vinylpyrrolidone-co-1-vinylimidazole) (such        as Sokalan HP56®).

Dye control agent Dye control agent in accordance with the invention,for example Suparex® O.IN (M1), Nylofixan® P (M2), Nylofixan® PM (M3),or Nylofixan® HF (M4)

-   -   HSAS is mid-branched alkyl sulfate as disclosed in U.S. Pat.        Nos. 6,020,303 and 6,060,443    -   LAS is linear alkylbenzenesulfonate having an average aliphatic        carbon chain length C₉-C₁₅ (HLAS is acid form).    -   Leuco colorant Any suitable leuco colorant or mixtures thereof        according to the instant invention.    -   Lipase is Lipex®, 18 mg active/g, supplied by Novozymes    -   Liquitint® V200 is a thiophene azo dye provided by Milliken    -   Mannanase is Mannaway®, 25 mg active/g, supplied by Novozymes    -   Nuclease is a Phosphodiesterase SEQ ID NO 1, reported as 1000 mg        active/g    -   Optical Brightener 1 is disodium 4,4′-bis        {[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate    -   Optical Brightener 2 is disodium        4,4′-bis-(2-sulfostyryl)biphenyl (sodium salt)    -   Optical Brightener 3 is Optiblanc SPL10® from 3V Sigma    -   Perfume encapsulate is a core-shell melamine formaldehyde        perfume microcapsules.    -   Polishing enzyme is Para-nitrobenzyl esterase, reported as 1000        mg active/g    -   Polymer 1 is        bis((C₂H₅O)(C₂H₄O)n)(CH₃)—N⁺—C_(x)H_(2x)—N⁺—(CH₃)—bis((C₂H₅O)(C₂H₄O)n),        wherein n=20-30, x=3 to 8 or sulphated or sulfonated variants        thereof    -   Polymer 2 is ethoxylated (EO₁₅) tetraethylene pentamine    -   Polymer 3 is ethoxylated polyethylenimine    -   Polymer 4 is ethoxylated hexamethylene diamine    -   Polymer 5 is Acusol 305, provided by Rohm&Haas    -   Polymer 6 is a polyethylene glycol polymer grafted with vinyl        acetate side chains, provided by BASF.

Protease is Purafect Prime®, 40.6 mg active/g, supplied by DuPont

-   -   Structurant is Hydrogenated Castor Oil

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

We claim:
 1. A compound of Formula (I)

wherein each individual R_(o) and R_(m) group on each of rings A, B andC is independently selected from the group consisting of hydrogen,deuterium and R⁵; wherein each R⁵ is independently selected from thegroup consisting of halogens, nitro, alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, substituted alkaryl, —(CH₂)_(n)—O—R¹,—(CH₂)_(n)—NR¹R², —C(O)R¹, —C(O)OR¹, —C(O)O⁻, —C(O)NR¹R², —OC(O)R¹,—OC(O)OR¹, —OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹, —S(O)₂O⁻, —S(O)₂NR¹R²,—NR¹C(O)R², —NR¹C(O)OR², —NR¹C(O)SR², —NR¹C(O)NR²R³, —P(O)₂R¹,—P(O)(OR¹)₂, —P(O)(OR¹)O⁻, and —P(O)(O⁻)₂, wherein the index n is aninteger from 0 to 4, preferably from 0 to 1, most preferably 0; whereinany two of R¹, R² and R³ attached to the same heteroatom can combine toform a ring of five or more members optionally comprising one or moreadditional heteroatoms selected from the group consisting of —O—,—NR¹⁵—, and —S—; wherein G is independently selected from the groupconsisting of hydrogen, deuterium, C₁-C₁₆ alkoxide, phenoxide,bisphenoxide, nitrite, alkyl amine, imidazole, arylamine, polyalkyleneoxide, halides, alkylsulfide, aryl sulfide, and phosphine oxide; whereinR¹, R², R³, and R¹⁵ are independently selected from the group consistingof hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl,substituted alkaryl, and R⁴; wherein R⁴ is a organic group composed ofone or more organic monomers with said monomer molecular weights rangingfrom 28 to 500; wherein one R_(p) is —NH₂ and the two remaining R_(p)are independently selected from the group consisting of —OR⁴ and —NR¹R⁴;and wherein any charge present in the compound is balanced with asuitable independently selected internal or external counterion.
 2. Thecompound of claim 1, wherein all four of the R_(o) and R_(m) on at leastone of the rings A, B, and C are hydrogen.
 3. The compound of claim 2,wherein all the R_(o) and R_(m) on all three rings A, B, and C arehydrogen.
 4. The compound of claim 3, wherein the two remaining R_(p)are independently selected —NR⁴R⁴.
 5. The compound of claim 1, whereineach R⁴ is an independently selected(C₂H₄O)_(x)(C₃H₆O)_(y)(C₂H₄O)_(z)R²⁰; R²⁰ is selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, aryl, substitutedaryl, alkaryl, and substituted alkaryl; the variables x, y, and z areintegers independently selected from 0 and the positive natural numbers;and the sum of x, y, and z is 1 or more.
 6. The compound of claim 5,wherein the variables x, y, and z are independently selected from 0 to100.
 7. The compound of claim 6, wherein the variables x, y, and z areindependently selected from 0 to
 20. 8. The compound of claim 7, whereinthe variables x, y, and z are independently selected from 0 to
 10. 9.The compound of claim 8, wherein the variable x is from 1 to 5, thevariable y is from 0 to 5, and the variable z is
 0. 10. The compound ofclaim 9, wherein the variable y is from 1 to
 5. 11. The compound ofclaim 9, wherein the variable x is from 1 to 2, and the variable y isfrom 0 to
 3. 12. The compound of claim 11, wherein the variable y isfrom 1 to
 3. 13. The compound of claim 5, wherein R²⁰ is hydrogen. 14.The compound of claim 1, wherein G is hydrogen or deuterium.
 15. Acompound of Formula (X)

wherein each individual R_(o) and R_(m) group on each of rings A, B andC is independently selected from the group consisting of hydrogen,deuterium and R⁵; wherein each R⁵ is independently selected from thegroup consisting of halogens, nitro, alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, substituted alkaryl, —(CH₂)_(n)—O—R¹,—(CH₂)_(n)—NR¹R², —C(O)R¹, —C(O)OR¹, —C(O)O⁻, —C(O)NR¹R², —OC(O)R¹,—OC(O)OR¹, —OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹, —S(O)₂O⁻, —S(O)₂NR¹R²,—NR¹C(O)R², —NR¹C(O)OR², —NR¹C(O)SR², —NR¹C(O)NR²R³, —P(O)₂R¹,—P(O)(OR¹)₂, —P(O)(OR)O⁻, and —P(O)(O⁻)₂, wherein the index n is aninteger from 0 to 4, preferably from 0 to 1, most preferably 0; whereinany two of R¹, R² and R³ attached to the same heteroatom can combine toform a ring of five or more members optionally comprising one or moreadditional heteroatoms selected from the group consisting of —O—,—NR¹⁵—, and —S—; wherein R¹, R², R³, and R¹⁵ are independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, substituted alkaryl, and R⁴; wherein R⁴ is aorganic group composed of one or more organic monomers with said monomermolecular weights ranging from 28 to 500; wherein one R_(p) is —NH₂ andthe two remaining R_(p) are independently selected from the groupconsisting of —OR⁴ and —NR¹R⁴; and wherein the charge present in thecompound is balanced with a suitable independently selected internal orexternal counterion.
 16. The compound of claim 15, wherein all four ofthe R_(o) and R_(m) on at least one of the rings A, B, and C arehydrogen.
 17. The compound of claim 16, wherein all the R_(o) and R_(m)on all three rings A, B, and C are hydrogen.
 18. The compound of claim17, wherein the two remaining R_(p) are independently selected —NR⁴R⁴.19. The compound of claim 15, wherein each R⁴ is an independentlyselected (C₂H₄O)_(x)(C₃H₆O)_(y)(C₂H₄O)_(z)R²⁰; R²⁰ is selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, substituted alkaryl; the variables x, y, andz are integers independently selected from 0 and the positive naturalnumbers; and the sum of x, y, and z is 1 or more.
 20. The compound ofclaim 19, wherein the variables x, y, and z are independently selectedfrom 0 to
 100. 21. The compound of claim 20, wherein the variables x, y,and z are independently selected from 0 to
 20. 22. The compound of claim21, wherein the variables x, y, and z are independently selected from 0to
 10. 23. The compound of claim 22, wherein the variable x is from 1 to5, the variable y is from 0 to 5, and the variable z is
 0. 24. Thecompound of claim 23, wherein the variable y is from 1 to
 5. 25. Thecompound of claim 23, wherein the variable x is from 1 to 2, and thevariable y is from 0 to
 3. 26. The compound of claim 25, wherein thevariable y is from 1 to
 3. 27. The compound of claim 19, wherein R²⁰ ishydrogen.
 28. The compound of claim 15, wherein the charge present inthe compound of Formula (X) is balanced by an external counterionselected from the group consisting of halides and sulfates.
 29. Thecompound of claim 15, wherein at least one of the R_(o) and R_(m) on atleast one of the rings A, B, and C is selected from —C(O)O⁻ and—S(O)₂O⁻.